Processing method, semiconductor device manufacturing method, processing apparatus, and recording medium

Abstract

The invention provides a processing method, a semiconductor device manufacturing method, a processing apparatus, and a recording medium. A film is selectively formed on a desired surface with high precision. The method comprises the steps of: (a) forming a first film containing a first element and a second element on the surface of a first substrate by supplying a first film-forming agent to the substrate having the first substrate and the second substrate on the surface thereof, and (b) forming a second film containing a second element on the surface of the first substrate by supplying a modifier to the substrate; a step (c) for forming a suppressor layer by supplying a second film-forming agent to the substrate on which the suppressor layer is formed on the surface of the first film, the suppressor layer being formed on the surface of the first substrate by causing at least a portion of the molecular structure of the molecules constituting the modifier to be adsorbed on the surface of the first film formed on the surface of the first substrate; and forming a second film containing the first element and the second element on the surface of the second substrate.

Description

Technical Field

[0001] The present disclosure relates to a processing method, a method for manufacturing a semiconductor device, a processing device, and a recording medium. Background Art

[0002] As a step in the manufacturing process of a semiconductor device, a process of selectively growing a film on a specific surface among multiple surfaces of different materials exposed on the surface of a substrate to form a film is sometimes performed (hereinafter, this process is also referred to as selective growth or selective film formation) (for example, refer to Patent Documents 1 to 3).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2021-106242

[0006] Patent Document 2: Japanese Patent Application Publication No. 2020-155452

[0007] Patent Document 3: Japanese Patent Application Publication No. 2020-155607 Summary of the invention

[0008] Problems to be solved by the invention

[0009] The present disclosure provides a technology for selectively forming a film on a desired surface with high precision.

[0010] Methods for solving problems

[0011] According to one embodiment of the present disclosure, a technology is provided, which includes the following steps:

[0012] (a) supplying a first film-forming agent to a substrate having a first base and a second base on a surface thereof, thereby forming a first film containing a first element and a second element on a surface of the first base,

[0013] (b) supplying a modifying agent to the substrate so that at least a part of the molecular structure of the molecules constituting the modifying agent is adsorbed on the surface of the first film formed on the surface of the first base to form an inhibitor layer, and

[0014] (c) supplying a second film-forming agent to the substrate having the inhibitor layer formed on the surface of the first film, thereby forming a second film containing the first element and the second element on the surface of the second base.

[0015] Effects of the Invention

[0016] According to the present disclosure, a film can be selectively formed on a desired surface with high precision. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a schematic configuration diagram of a vertical processing furnace of a processing device preferably used in one embodiment of the present disclosure, and is a diagram showing a processing furnace 202 portion in a longitudinal cross-sectional view.

[0018] Figure 2 This is a schematic diagram of a vertical processing furnace of a processing device preferably used in one embodiment of the present disclosure. Figure 1 The AA line cross-sectional view shows a portion of the processing furnace 202 .

[0019] Figure 3 1 is a schematic configuration diagram of a controller 121 of a processing device preferably used in one embodiment of the present disclosure, and is a diagram showing a control system of the controller 121 in the form of a block diagram.

[0020] Figure 4 middle, Figure 4 (a) is a schematic cross-sectional view showing a surface portion of a wafer having a first substrate and a second substrate on the surface; Figure 4 (b) shows that by Figure 4 (a) is a schematic cross-sectional view of a surface portion of a wafer after step A is performed to selectively form a first film on the surface of a first substrate; Figure 4 (c) is a diagram showing that Figure 4 (b) is a schematic cross-sectional view of a surface portion of the wafer after step B is performed and an inhibitor layer is formed on the surface of the first film formed on the surface of the first substrate; Figure 4 (d) is a diagram showing that Figure 4 (c) is a schematic cross-sectional view of a surface portion of the wafer after the second film is selectively formed on the surface of the second substrate by performing step C; Figure 4 (e) is a diagram showing that Figure 4 (d) is a schematic cross-sectional view of the surface portion of the wafer after the step D is performed to remove the first film formed on the surface of the first substrate together with the inhibitor layer.

[0021] Figure 5 middle, Figure 5 (a)~ Figure 5 (d) are respectively Figure 4 (a)~ Figure 4 (d) The same figure; Figure 5 (e) is a diagram showing that Figure 5 (d) is a schematic cross-sectional view of a surface portion of the wafer after step E is performed to selectively form a third film on the surface of the second film formed on the surface of the second substrate; Figure 5 (f) is a diagram showing that Figure 5(e) is a schematic cross-sectional view of the surface portion of the wafer after the step D is performed to remove the first film formed on the surface of the first substrate together with the inhibitor layer.

[0022] Description of Reference Numerals

[0023] 200: Wafer (substrate). DETAILED DESCRIPTION

[0024] <One aspect of the present disclosure>

[0025] The following mainly refers to Figure 1 to Figure 3 , Figure 4 (a)~ Figure 4 (e) One embodiment of the present disclosure is described. In addition, the drawings used in the following description are all schematic drawings, and the relationship between the dimensions of the elements and the ratio of the elements shown in the drawings may not be consistent with the actual situation. In addition, the relationship between the dimensions of the elements and the ratio of the elements may not be consistent between multiple drawings.

[0026] (1) Configuration of processing device (processing system)

[0027] like Figure 1 As shown in FIG. 1 , the processing furnace 202 of the processing device has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is vertically installed by being supported by a holding plate. The heater 207 functions as an energy imparting unit that imparts energy to the gas, and also functions as an activation mechanism (excitation unit) when the gas is activated (excited) by heat.

[0028] On the inner side of the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS), and is formed into a cylindrical shape with an open upper end and a lower end. The upper end of the manifold 209 is engaged with the lower end of the reaction tube 203, and is configured to support the reaction tube 203. An O-ring 220a as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically in the same manner as the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing container (reaction container). A processing chamber 201 is formed in the hollow portion of the cylinder of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. The wafer 200 is processed in the processing chamber 201 .

[0029] Nozzles 249a to 249c are provided as first to third supply parts in the processing chamber 201 so as to penetrate the side wall of the manifold 209. The nozzles 249a to 249c are also referred to as first to third nozzles. The nozzles 249a to 249c are made of heat-resistant materials such as quartz or SiC, for example. The nozzles 249a to 249c are connected to the gas supply pipes 232a to 232c, respectively. The nozzles 249a to 249c are different nozzles, and the nozzles 249a and 249c are respectively provided adjacent to the nozzle 249b.

[0030] In the gas supply pipes 232a to 232c, mass flow controllers (MFC) 241a to 241c as flow controllers (flow control units) and valves 243a to 243c as on-off valves are respectively provided in order from the upstream side of the gas flow. Gas supply pipes 232d, 232e, and 232h are respectively connected to the downstream side of the gas supply pipe 232a relative to the valve 243a. Gas supply pipes 232f and 232g are respectively connected to the downstream side of the gas supply pipes 232b and 232c relative to the valves 243b and 243c. In the gas supply pipes 232d to 232h, MFCs 241d to 241h and valves 243d to 243h are respectively provided in order from the upstream side of the gas flow. The gas supply pipes 232a to 232h are made of metal materials such as SUS, for example.

[0031] like Figure 2As shown, the nozzles 249a to 249c are respectively arranged in a circular space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, so as to stand upward in the arrangement direction of the wafer 200 along the inner wall of the reaction tube 203 at a position higher than the lower part. That is, the nozzles 249a to 249c are respectively arranged in a region that horizontally surrounds the wafer arrangement region on the side of the wafer arrangement region where the wafers 200 are arranged in a manner along the wafer arrangement region. In a plan view, the nozzle 249b is arranged so as to face the exhaust port 231a described later on a straight line across the center of the wafer 200 carried into the processing chamber 201. The nozzles 249a and 249c are arranged so as to sandwich a straight line L passing through the center of the nozzle 249b and 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. That is, the nozzle 249c may be arranged on the opposite side of the nozzle 249a across the straight line L. The nozzles 249a and 249c are arranged line-symmetrically with the straight line L as the axis of symmetry. Gas supply holes 250a to 250c for supplying gas are respectively provided on the side surfaces of the nozzles 249a to 249c. The gas supply holes 250a to 250c are respectively opened in a manner opposite (facing) to the exhaust port 231a when viewed from above, and can supply gas toward the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the bottom to the top of the reaction tube 203.

[0032] Raw materials, namely, a first raw material, a second raw material, and a third raw material are supplied from the gas supply pipe 232a via the MFC 241a, the valve 243a, and the nozzle 249a into the processing chamber 201. The first raw material is used as one of the first film-forming agents. The second raw material is used as one of the second film-forming agents. The third raw material is used as one of the third film-forming agents.

[0033] Catalysts, namely, the first catalyst, the second catalyst, and the third catalyst, are supplied from the gas supply pipe 232b via the MFC 241b, the valve 243b, and the nozzle 249b into the processing chamber 201. The first catalyst is used as one of the first film-forming agents. The second catalyst is used as one of the second film-forming agents. The third catalyst is used as one of the third film-forming agents.

[0034] Oxidants, namely, a first oxidant, a second oxidant, and a third oxidant, are supplied from the gas supply pipe 232c via the MFC 241c, the valve 243c, and the nozzle 249c into the processing chamber 201. The first oxidant is used as one of the first film-forming agents. The second oxidant is used as one of the second film-forming agents. The third oxidant is used as one of the third film-forming agents.

[0035] The modifying agent is supplied into the processing chamber 201 from the gas supply pipe 232d via the MFC 241d, the valve 243d, the gas supply pipe 232a, and the nozzle 249a.

[0036] The etchant is supplied into the processing chamber 201 from the gas supply pipe 232h via the MFC 241h, the valve 243h, the gas supply pipe 232a, and the nozzle 249a.

[0037] Inert gas is supplied from gas supply pipes 232e to 232g into the processing chamber 201 via MFCs 241e to 241g, valves 243e to 243g, gas supply pipes 232a to 232c, and nozzles 249a to 249c. The inert gas functions as a purge gas, a carrier gas, a dilution gas, and the like.

[0038] The raw material supply system (first raw material supply system, second raw material supply system, third raw material supply system) is mainly composed of the gas supply pipe 232a, MFC 241a, and valve 243a. The catalyst supply system (first catalyst supply system, second catalyst supply system, third catalyst supply system) is mainly composed of the gas supply pipe 232b, MFC 241b, and valve 243b. The oxidant supply system (first oxidant supply system, second oxidant supply system, third oxidant supply system) is mainly composed of the gas supply pipe 232c, MFC 241c, and valve 243c. The raw material supply system (first raw material supply system, second raw material supply system, third raw material supply system), the catalyst supply system (first catalyst supply system, second catalyst supply system, third catalyst supply system), and the oxidant supply system (first oxidant supply system, second oxidant supply system, third oxidant supply system) are also referred to as the film-forming agent supply system (first film-forming agent supply system, second film-forming agent supply system, third film-forming agent supply system). The modifier supply system is mainly composed of the gas supply pipe 232d, MFC 241d, and valve 243d. The etchant supply system is mainly composed of the gas supply pipe 232h, MFC 241h, and valve 243h. The inert gas supply system is mainly composed of the gas supply pipes 232e to 232g, MFC 241e to 241g, and valves 243e to 243g.

[0039] Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which valves 243a to 243h, MFCs 241a to 241h, etc. are integrated. The integrated supply system 248 is connected to the gas supply pipes 232a to 232h, respectively, and is configured so that the supply operation of various substances (various gases) into the gas supply pipes 232a to 232h is controlled by the controller 121 described later, that is, the opening and closing operation of the valves 243a to 243h, the flow rate adjustment operation performed by the MFCs 241a to 241h, etc. The integrated supply system 248 is configured as an integrated unit of an integral type or a split type, and can be attached and detached relative to the gas supply pipes 232a to 232h, etc., as an integrated unit, and can be maintained, replaced, and added as an integrated unit.

[0040] An exhaust port 231a is provided below the side wall of the reaction tube 203 to exhaust the atmosphere in the processing chamber 201. Figure 2 As shown, the exhaust port 231a is arranged at a position opposite (facing) the nozzles 249a to 249c (gas supply holes 250a to 250c) across the wafer 200 when viewed from above. The exhaust port 231a can also be arranged along a position higher than the lower part of the side wall of the reaction tube 203, that is, along the wafer arrangement area. The exhaust port 231a is connected to the exhaust pipe 231. On the exhaust pipe 231, a vacuum pump 246 as a vacuum exhaust device is connected 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 regulating unit). The APC valve 244 is configured to open and close the valve while the vacuum pump 246 is in operation, thereby enabling vacuum exhaust and vacuum exhaust stop in the processing chamber 201, and to adjust the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is in operation, thereby enabling the pressure in the processing chamber 201 to be adjusted. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may also be included in the exhaust system.

[0041] A sealing cover 219 as a furnace cover body capable of hermetically closing the lower end opening of the manifold 209 is provided below the manifold 209. The sealing cover 219 is made of a metal material such as SUS and is formed into a disc shape. An O-ring 220b as a sealing component abutting against the lower end of the manifold 209 is provided on the upper surface of the sealing cover 219. A rotating mechanism 267 for rotating the wafer box 217 described later is provided below the sealing cover 219. The rotating shaft 255 of the rotating mechanism 267 passes through the sealing cover 219 and is connected to the wafer box 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer box 217. The sealing cover 219 is configured to be lifted and lowered in the vertical direction by a wafer box elevator 115 as a lifting mechanism provided outside the reaction tube 203. The cassette elevator 115 is configured as a transport device (transport mechanism) that carries the wafer 200 in and out (transports) the wafer 200 into and out of the processing chamber 201 by raising and lowering the sealing cover 219 .

[0042] A baffle 219s is provided below the manifold 209 as a furnace cover, and the lower end opening of the manifold 209 can be hermetically sealed when the sealing cover 219 is lowered and the wafer box 217 is carried out from the processing chamber 201. The baffle 219s is made of a metal material such as SUS and is formed into a disc shape. An O-ring 220c as a sealing member abutting against the lower end of the manifold 209 is provided on the upper surface of the baffle 219s. The opening and closing action (lifting action, rotation action, etc.) of the baffle 219s is controlled by the baffle opening and closing mechanism 115s.

[0043] The wafer box 217 as a substrate support is configured to support multiple (e.g., 25 to 200) wafers 200 in a horizontal posture and arranged in a vertical direction with their centers aligned with each other in multiple layers, that is, arranged at intervals. The wafer box 217 is made of, for example, a heat-resistant material such as quartz or SiC. At the bottom of the wafer box 217, a heat insulation plate 218 made of, for example, a heat-resistant material such as quartz or SiC is supported in multiple layers.

[0044] A temperature sensor 263 as a temperature detector is provided in the reaction tube 203. The temperature in the processing chamber 201 is set to a desired temperature distribution by adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0045] like Figure 3As shown, the controller 121 as a control unit (control unit) is configured as a computer having a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c and an I / O interface 121d. The RAM 121b, the storage device 121c, and the I / O interface 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. The controller 121 is connected to an input / output device 122 such as a touch panel. In addition, the controller 121 can be connected to an external storage device 123. It should be noted that the processing device can be configured to have one control unit or multiple control units. That is, the control for performing the processing flow described later can be performed using one control unit or multiple control units. In addition, multiple control units can be configured as a control system interconnected by a wired or wireless communication network, or the control for performing the processing flow described later can be performed by the control system as a whole. In this specification, when the term "control unit" is used, it may include not only a case where one control unit is included but also a case where a plurality of control units are included or a control system is constituted by a plurality of control units.

[0046] The storage device 121c is composed of, for example, a flash memory, a HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. In the storage device 121c, a control program for controlling the action of the processing device, a process recipe recording the process and conditions of the processing described later, etc. are recorded and stored in a readable manner. The process recipe is a combination of a process that enables the processing device (processing system) to execute each process in the processing described later and obtain a specified result through the controller 121, and functions as a program. Hereinafter, process recipes, control programs, etc. are collectively referred to as programs. In addition, process recipes are also referred to as recipes. When the word "program" is used in this specification, sometimes only the recipe is included alone, sometimes only the control program is included alone, or sometimes both are included. RAM 121b is configured as a storage area (working area) for temporarily holding programs, data, etc. read out by CPU 121a.

[0047] The I / O interface 121d is connected to the MFCs 241a to 241h, valves 243a to 243h, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, wafer box elevator 115, shutter opening and closing mechanism 115s, etc.

[0048] The CPU 121a is configured to read out a control program from the storage device 121c and execute it, and to read out a recipe from the storage device 121c according to input of an operation command from the input / output device 122. The CPU 121a is configured to control, according to the contents of the read recipe, flow rate adjustment operations of various substances (various gases) by the MFCs 241a to 241h, opening and closing operations of the valves 243a to 243h, opening and closing operations of the APC valve 244 and pressure adjustment operations by the APC valve 244 based on the pressure sensor 245, start and stop of the vacuum pump 246, temperature adjustment operations of the heater 207 based on the temperature sensor 263, rotation of the wafer cassette 217 and rotation speed adjustment operations by the rotation mechanism 267, lifting and lowering operations of the wafer cassette 217 by the wafer cassette elevator 115, opening and closing operations of the shutter 219s by the shutter opening and closing mechanism 115s, and the like.

[0049] The controller 121 can be configured by installing the above-mentioned program recorded and stored in the external storage device 123 on a computer. The external storage device 123 includes, for example, a disk such as an HDD, an optical disk such as a CD, an optical disk such as an MO, a semiconductor memory such as a USB memory, an SSD, etc. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, they are collectively referred to as a recording medium. In this specification, when the term "recording medium" is used, sometimes only the storage device 121c is included alone, sometimes only the external storage device 123 is included alone, or sometimes both of them are included. It should be noted that it is also possible to provide the program to the computer using a communication unit such as the Internet or a dedicated line instead of using the external storage device 123.

[0050] (2) Processing

[0051] The present invention relates to a method for processing a substrate (processing method) as one step of a manufacturing process (manufacturing method) of a semiconductor device using the above-mentioned processing apparatus, that is, an example of a processing flow for selectively forming a film on the surface of a first substrate and a second substrate of a surface of a wafer 200 as a substrate, mainly using Figure 4 (a)~ Figure 4 (e) is described. In the following description, the operation of each part constituting the processing device is controlled by the controller 121. In addition, the processing device is also referred to as a substrate processing device, a film forming processing device, or a film forming device. In addition, the processing method is also referred to as a substrate processing method, a film forming processing method, or a film forming method.

[0052] It should be noted that if Figure 4As shown in (a), the wafer 200 as a substrate has a first base and a second base on the surface. In the following description, for convenience, as a representative example, the case where the first base is a silicon nitride film (SiN film) and the second base is a silicon film (Si film) is described.

[0053] In the processing flow of this method, the following steps are performed: (a) step A of forming a first film containing a first element and a second element on the surface of a wafer 200 having a first substrate and a second substrate on its surface by supplying a first film-forming agent; (b) step B of forming an inhibitor layer by supplying a modifier to the wafer 200 so that at least a portion of the molecular structure of the molecules constituting the modifier is adsorbed on the surface of the first film formed on the surface of the first substrate; and (c) step C of forming a second film containing the first element and the second element on the surface of the second substrate by supplying a second film-forming agent to the wafer 200 having an inhibitor layer formed on the surface of the first film.

[0054] Hereinafter, in step A, a case where a first raw material, a first oxidant, and a first catalyst are supplied to the wafer 200 as a first film-forming agent, and in step C, a case where a second raw material, a second oxidant, and a second catalyst are supplied to the wafer 200 as a second film-forming agent is described. Specifically, in step A, a cycle including step A1 (a1) supplying the first raw material and the first catalyst to the wafer 200 and step A2 (a2) supplying the first oxidant and the first catalyst to the wafer 200 is performed a predetermined number of times (m times, m is an integer greater than or equal to 1 or 2), and in step C, a cycle including step C1 (c1) supplying the second raw material and the second catalyst to the wafer 200 and step C2 (c2) supplying the second oxidant and the second catalyst to the wafer 200 is performed a predetermined number of times (n times, n is an integer greater than or equal to 1 or 2) is described.

[0055] It should be noted that, in at least one of step A1 and step A2, the supply of the first catalyst can be omitted according to the processing conditions, and in at least one of step C1 and step C2, the supply of the second catalyst can also be omitted. For example, the supply of the first catalyst can be omitted in step A1, the supply of the first catalyst can be omitted in step A2, or the supply of the first catalyst can be omitted in step A1 and step A2, respectively. For example, in this step, as the first film-forming agent, the first raw material and the first oxidant can be used. In addition, for example, the supply of the second catalyst can be omitted in step C1, the supply of the second catalyst can be omitted in step C2, or the supply of the second catalyst can be omitted in step C1 and step C2, respectively. For example, in this step, as the second film-forming agent, the second raw material and the second oxidant can also be used.

[0056] In the following example, a case is described in which the process (d) further includes supplying an etchant to the wafer 200 after forming the second film on the surface of the second substrate to remove the first film. The process performed in step D is also referred to as etch back.

[0057] In this specification, for convenience, the above-mentioned processing flow may be expressed as follows. The same expression is also used in the following description of modified examples, other aspects, etc.

[0058] (first raw material + first catalyst → first oxidant + first catalyst) × m → modifier → (second raw material + second catalyst → second oxidant + second catalyst) × n → etchant (etch back))

[0059] The term "wafer" used in this specification sometimes means the wafer itself, and sometimes means a stack of a wafer and a predetermined layer or film formed on its surface. The term "surface of the wafer" used in this specification sometimes means the surface of the wafer itself, and sometimes means the surface of a predetermined layer, etc. formed on the wafer. When it is stated in this specification that "a predetermined layer is formed on the wafer", it sometimes means that a predetermined layer is directly formed on the surface of the wafer itself, and sometimes means that a predetermined layer is formed on a layer, etc. formed on the wafer. In this specification, the use of the word "substrate" is synonymous with the use of the word "wafer".

[0060] The term "layer" used in this specification includes at least one of a continuous layer and a discontinuous layer. For example, the first layer, the second layer, the third layer, the fourth layer, and the inhibitor layer may each include a continuous layer, a discontinuous layer, or both.

[0061] The term "agent" 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, the first film-forming agent (first raw material, first oxidant, first catalyst), the second film-forming agent (second raw material, second oxidant, second catalyst), the third film-forming agent (third raw material, third oxidant, third catalyst), the modifier, and the etchant may include a gaseous substance, a liquid substance such as a mist substance, or both.

[0062] (Wafer loading and wafer cassette loading)

[0063] When a plurality of wafers 200 are loaded (wafer loading) into the wafer box 217, the shutter 219s is moved by the shutter opening and closing mechanism 115s, and the lower end opening of the manifold 209 is opened (the shutter is opened). Figure 1As shown, the wafer cassette 217 supporting a plurality of wafers 200 is lifted by the wafer cassette elevator 115 and carried into the processing chamber 201 (wafer cassette loading). In this state, the sealing cap 219 seals the lower end of the manifold 209 via the O-ring 220b. In this way, the wafers 200 are prepared in the processing chamber 201.

[0064] (Pressure adjustment and temperature adjustment)

[0065] After the wafer box is loaded, vacuum pump 246 is used to perform vacuum exhaust (decompression exhaust) so that the space in the processing chamber 201, that is, the space where the wafer 200 exists, becomes the desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by pressure sensor 245, and feedback control is performed on APC valve 244 based on the measured pressure information. In addition, heating is performed by heater 207 so that the wafer 200 in the processing chamber 201 becomes the desired processing temperature. At this time, feedback control is performed on the power supply to heater 207 based on the temperature information detected by temperature sensor 263 so that the temperature distribution in the processing chamber 201 becomes the desired temperature distribution. In addition, the rotation mechanism 267 starts to rotate the wafer 200. The exhaust in the processing chamber 201, the heating and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.

[0066] (Step A)

[0067] Then, the first film-forming agent is supplied to the wafer 200 having the first and second bases on the surface thereof, so that the first film containing the first element and the second element is formed on the surface of the first base. In this step, specifically, the following steps A1 and A2 are sequentially performed.

[0068] [Step A1]

[0069] In this step, the first raw material and the first catalyst are supplied to the wafer 200 .

[0070] Specifically, valves 243a and 243b are opened to allow the first raw material and the first catalyst to flow into gas supply pipes 232a and 232b, respectively. The first raw material and the first catalyst are respectively regulated by MFC 241a and MFC 241b, and are respectively supplied into the processing chamber 201 through nozzles 249a and 249b, mixed in the processing chamber 201, and exhausted from the exhaust port 231a. At this time, the first raw material and the first catalyst are supplied to the wafer 200 from the side of the wafer 200 (first raw material + first catalyst supply). At this time, valves 243e to 243g may also be opened to supply inactive gas into the processing chamber 201 through nozzles 249a to 249c, respectively.

[0071] By supplying the first raw material and the first catalyst to the wafer 200 under the processing conditions described below, at least a portion of the molecular structure of the molecules constituting the first raw material can be selectively (preferentially) chemically adsorbed on the surface of the first substrate between the surface of the first substrate and the surface of the second substrate. Thus, a first layer is selectively formed on the surface of the first substrate. The first layer contains residues from the first raw material, that is, at least a portion of the molecular structure of the molecules constituting the first raw material.

[0072] In this step, in order to selectively form the first layer on the surface of the first substrate, when the first raw material as the first film-forming agent is used to form the first layer, the property that the incubation time on the surface of the second substrate is longer than the incubation time on the surface of the first substrate is utilized. The surface of the SiN film as the first substrate has NH terminals and OH terminals, and the surface of the Si film as the second substrate has H terminals. When forming the first layer, the incubation time on the H terminals on the surface of the Si film is longer than the incubation time on the NH terminals and OH terminals on the surface of the SiN film. That is, it is difficult to form the first layer on the surface of the Si film containing the H terminals compared to the surface of the SiN film containing the NH terminals and OH terminals. Therefore, in this step, the first layer can be selectively (preferentially) formed on the surface of the SiN film as the first substrate and the surface of the Si film as the second substrate. In addition, according to such a situation, when it is desired to form the first layer on the surface containing the NH terminals, OH terminals, and H terminals, it can also be said that the H terminals and the surface containing the H terminals produce a film formation inhibitory effect (adsorption inhibitory effect, reaction inhibitory effect).

[0073] It should be noted that in order to reliably expose the H terminal on the surface of the Si film as the second substrate, the surface of the wafer 200 may be exposed to an etchant such as an HF aqueous solution (DHF) in advance. Sometimes a natural oxide film is formed on the surface of the Si film as the second substrate. In this case, by exposing the surface of the wafer 200 to an etchant, the natural oxide film on the surface of the Si film can be removed, and the H terminal can be reliably exposed on the surface of the Si film. It should be noted that sometimes a natural oxide film is formed on the surface of the SiN film as the first substrate. In this case, by exposing the surface of the wafer 200 to an etchant, the natural oxide film on the surface of the SiN film can also be removed, and the NH terminal and the OH terminal can be appropriately exposed on the surface of the SiN film. It should be noted that as an etchant, the same etchant as that used in step D described later can be used, and the etching treatment at this time can be performed by the same processing procedure and processing conditions as the etching treatment in step D described later.

[0074] The following are examples of treatment conditions when the first raw material and the first catalyst are supplied in this step.

[0075] Treatment temperature: room temperature (25°C) to 200°C, preferably 25 to 150°C,

[0076] Processing pressure: 13-2666Pa, preferably 13-1333Pa,

[0077] Processing time: 1 to 90 seconds, preferably 1 to 60 seconds,

[0078] First raw material supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm,

[0079] First catalyst supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm,

[0080] Inert gas supply flow rate (per gas supply pipe): 0~20slm

[0081] It should be noted that the expression of a numerical range such as "25 to 200°C" in this specification means that the lower limit and the upper limit are included in the range. Therefore, for example, "25 to 200°C" means "above 25°C and below 200°C". The same applies to other numerical ranges. In addition, the processing temperature in this specification refers to the temperature of the wafer 200 or the temperature in the processing chamber 201, and the processing pressure refers to the pressure in the processing chamber 201. In addition, the processing time refers to the time during which the processing continues. In addition, when the supply flow rate includes 0 slm (sccm), 0 slm (sccm) means that the gas is not supplied. These are also the same in the following descriptions.

[0082] After the first layer is selectively formed on the surface of the first substrate, the valves 243a and 243b are closed to stop supplying the first raw material and the first catalyst into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove the gaseous substances and the like remaining in the processing chamber 201 from the processing chamber 201. At this time, the valves 243e to 243g are opened to supply an inert gas into the processing chamber 201 through the nozzles 249a to 249c. The inert gas supplied from the nozzles 249a to 249c acts as a purge gas, and thus, the processing chamber 201 is purged (purged).

[0083] The following are examples of treatment conditions when purging is performed in this step.

[0084] Processing pressure: 1~30Pa,

[0085] Processing time: 1 to 120 seconds, preferably 1 to 60 seconds,

[0086] Inert gas supply flow rate (per gas supply pipe): 0.5~20slm

[0087] It should be noted that the treatment temperature during the purging is preferably the same temperature as the treatment temperature during the supply of the first raw material and the first catalyst.

[0088] As the first raw material, for example, a substance (gas) containing at least any one of an amino group, an alkoxy group, and a chloro group can be used. The substance (gas) containing at least any one of an amino group, an alkoxy group, and a chloro group is preferably a substance (gas) that also contains silicon (Si). The first raw material can be selected according to the type of the first substrate. For example, in the case where the first substrate is a metal element single substance film, it is preferred to select a substance (gas) having an amino group and Si.

[0089] As the first raw material, for example, substances (gases) containing amino groups and Si, such as tetrakis(dimethylamino)silane (Si[N(CH3)2]4), tris(dimethylamino)silane (Si[N(CH3)2]3H), bis(diethylamino)silane (Si[N(C2H5)2]2H), bis(tert-butylamino)silane (SiH2[NH(C4H9)]2), and (diisopropylamino)silane (SiH3[N(C3H7)2]) can be used.

[0090] In addition, as the first raw material, for example, a substance (gas) containing an alkoxy group and Si, such as tetramethoxysilane (Si(OCH3)4) and tetraethoxysilane (Si(OC2H5)4) can be used. In addition, as the first raw material, for example, a substance (gas) containing an alkoxy group, an amino group and Si, such as (dimethylamino)trimethoxysilane ((CH3)2NSi(OCH3)3) and (dimethylamino)triethoxysilane ((CH3)2NSi(OC2H5)3) can also be used. As the first raw material, one or more of them can be used.

[0091] In addition, as the first raw material, for example, bis(trichlorosilyl)methane ((SiCl3)2CH2), 1,2-bis(trichlorosilyl)ethane ((SiCl3)2C2H4), 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH3)2Si2Cl4), 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH3)4Si2Cl2), 1,1,3,3-tetrachloro-1,3-disilacyclobutane (C2H4Cl4Si2) and other substances (gases) containing chlorine groups and Si can be used. These substances also contain alkylene groups or alkyl groups. In addition, as the first raw material, for example, silicon tetrachloride (SiCl4), hexachlorodisilane (Si2Cl6), octachlorotrisilane (Si3Cl8) and other substances (gases) containing chlorine groups and Si can be used. In addition, as the first raw material, for example, hexachlorodisiloxane (Cl3Si-O-SiCl3), octachlorotrisiloxane (Cl3Si-O-SiCl2-O-SiCl3) and other substances (gases) containing chlorine groups and Si can be used. These substances also contain oxygen. As the first raw material, one or more of them can be used.

[0092] As the first catalyst, for example, an amine-based substance (amine-based gas) containing carbon (C), nitrogen (N) and hydrogen (H) can be used. As the amine-based substance, a cyclic amine-based substance (cyclic amine-based gas) or a chain amine-based substance (chain amine-based gas) can be used. As the first catalyst, for example, pyridine (C5H5N), aminopyridine (C5H6N2), picoline (C6H7N), lutidine (C7H9N), pyrimidine (C4H4N2), quinoline (C9H7N), piperazine (C4H 10 N2), piperidine (C5H 11 N), pyrrolidine (C4H9N), aniline (C6H7N) and other cyclic amine substances (cyclic amine gases). In addition, as the first catalyst, for example, triethylamine ((C2H5)3N), diethylamine ((C2H5)2NH), monoethylamine ((C2H5)NH2), trimethylamine ((CH3)3N), dimethylamine ((CH3)2NH), monomethylamine ((CH3)NH2) and other chain amine substances (chain amine gases) can be used. As the first catalyst, one or more of them can be used.

[0093] As the inert gas, for example, inert gases such as nitrogen (N2), argon (Ar), helium (He), neon (Ne), and xenon (Xe) can be used. As the inert gas, one or more of them can be used. This also applies to each step described later.

[0094] [Step A2]

[0095] After step A1 is completed, the first oxidizing agent and the first catalyst are supplied to the wafer 200 .

[0096] Specifically, valves 243c and 243b are opened to allow the first oxidant and the first catalyst to flow into the gas supply pipes 232c and 232b, respectively. The first oxidant and the first catalyst are respectively regulated by MFC 241c and MFC 241b, and are respectively supplied into the processing chamber 201 through nozzles 249c and 249b, mixed in the processing chamber 201, and exhausted from the exhaust port 231a. At this time, the first oxidant and the first catalyst are supplied to the wafer 200 from the side of the wafer 200 (first oxidant + first catalyst supply). At this time, valves 243e to 243g may also be opened to supply inactive gas into the processing chamber 201 through nozzles 249a to 249c, respectively.

[0097] By supplying the first oxidant and the first catalyst to the wafer 200 under the processing conditions described below, at least a portion of the first layer formed on the surface of the first base in step A1 can be oxidized. Thus, a second layer formed on the surface of the first base by oxidizing the first layer.

[0098] The following are examples of treatment conditions when the first oxidizing agent and the first catalyst are supplied in this step.

[0099] Treatment temperature: room temperature (25°C) to 200°C, preferably 25 to 150°C,

[0100] Processing pressure: 13-2666Pa, preferably 13-1333Pa,

[0101] Processing time: 1 to 90 seconds, preferably 1 to 60 seconds,

[0102] First oxidant supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm,

[0103] First catalyst supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm,

[0104] Inert gas supply flow rate (per gas supply pipe): 0~20slm

[0105] After the first layer formed on the surface of the first substrate is oxidized and changed (converted) to the second layer, the valves 243c and 243b are closed to stop supplying the first oxidant and the first catalyst into the processing chamber 201. Then, according to the same processing process and processing conditions as those in the purge in step A1, the gaseous substances and the like remaining in the processing chamber 201 are removed (purged) from the processing chamber 201. It should be noted that the processing temperature during the purge is preferably the same temperature as the processing temperature during the supply of the first oxidant and the first catalyst.

[0106] As the first oxidant, for example, a substance containing oxygen (O) and hydrogen (H) (gas containing O and H) can be used. As the first oxidant, for example, a substance containing O and H (gas containing O and H) such as water vapor (H2O), hydrogen peroxide (H2O2), hydrogen (H2) + oxygen (O2), H2 + ozone (O3) can be used. That is, as a substance containing O and H, an O-containing substance + a H-containing substance can also be used. In this case, as a substance containing H, deuterium (D2) can also be used instead of H2. As the first oxidant, one or more of these can be used.

[0107] It should be noted that, in this specification, the description of two substances such as "H2+O2" refers to a mixed substance (mixed gas) of H2 and O2. When supplying a mixed substance (mixed gas), the two substances can be mixed (pre-mixed) in a supply pipe and then supplied to the processing chamber 201, or the two substances can be supplied to the processing chamber 201 from different supply pipes and mixed (post-mixed) in the processing chamber 201.

[0108] As the first catalyst, for example, the same catalysts as the various first catalysts exemplified in the above step A1 can be used.

[0109] [Number of times the regulations are implemented]

[0110] The cycle including the above-mentioned step A1 and step A2, specifically, the cycle of performing step A1 and step A2 non-simultaneously (alternatingly) is performed a predetermined number of times (m times, where m is an integer greater than 1 or 2). Figure 4 As shown in (b), a first film containing a first element and a second element can be selectively formed on the surface of the first substrate of the surface of the first substrate and the surface of the second substrate of the wafer 200. For example, when the above-mentioned first raw material, the first oxidant and the first catalyst are used, a silicon oxide film (SiO film), a silicon oxide film (SiOC film) or a silicon oxide film (SiOCN film) as an oxide film can be selectively grown on the surface of the first substrate. In this way, on the surface of the first substrate, for example, a first film in which the first element is silicon (Si) and the second element is oxygen (O) can be selectively grown. The first film may also contain carbon (C) and nitrogen (N).

[0111] In other words, the thickness of the second layer formed in each cycle is preferably thinner than the desired thickness of the first film, and the above cycle is repeated multiple times until the thickness of the first film formed by laminating the second layer reaches the desired thickness.

[0112] It should be noted that, when implementing step A1 and step A2, sometimes the formation and growth of the first film on the surface of the second substrate occurs very rarely. However, even in this case, the thickness of the first film formed on the surface of the second substrate is much thinner than the thickness of the first film formed on the surface of the first substrate. In this specification, "selectively (preferentially) forming the first film on the surface of the first substrate" includes not only the case where the first film is not formed at all on the surface of the second substrate and the first film is formed only on the surface of the first substrate, but also the case where an extremely thin first film is formed on the surface of the second substrate, but a first film much thicker than the first film is formed on the surface of the first substrate.

[0113] In this step, the thickness of the first film formed on the surface of the first substrate is preferably 0.5 nm to 10 nm, preferably 1 nm to 5 nm, and more preferably 1.5 nm to 3 nm.

[0114] If the thickness of the first film is less than 0.5nm, then in step B described later, the amount of at least a portion of the molecular structure of the molecules of the modifier adsorbed on the surface of the first film (residues from the modifier) ​​is sometimes insufficient. In this case, the adsorption inhibition effect of the inhibitor layer formed on the surface of the first film is sometimes insufficient. This problem can be solved by setting the thickness of the first film to be greater than 0.5nm. This problem can be effectively eliminated by setting the thickness of the first film to be greater than 1nm. This problem can be more effectively eliminated by setting the thickness of the first film to be greater than 1.5nm.

[0115] If the thickness of the first film is made thicker than 10nm, the adsorption inhibition effect of at least a part of the H terminal in the surface of the second substrate is invalidated due to the effect of the first film-forming agent, and the adsorption inhibition effect of the H terminal sometimes becomes insufficient. As a result, the first film is sometimes formed on the surface of the second substrate, and the inhibitor layer is also formed on the surface of the second substrate in the next step B. This problem can be eliminated by setting the thickness of the first film to less than 10nm. This problem can be effectively eliminated by setting the thickness of the first film to less than 5nm. This problem can be more effectively eliminated by setting the thickness of the first film to less than 3nm.

[0116] The thickness of the first film formed in this step may be the same as or different from the thickness of the second film formed in step C described later. It should be noted that in this step, the thickness of the first film is preferably set to be less than the thickness of the second film formed in step C described later, and more preferably set to be thinner than the thickness of the second film formed in step C. That is, in this step, it is preferred to make the thickness of the first film different from the thickness of the second film formed in step B, and more preferably make the thickness of the first film thinner than the thickness of the second film. As a result, the film thickness difference between the first film formed on the surface of the first substrate and the second film formed on the surface of the second substrate (i.e., the thickness of the second film-the thickness of the first film) becomes larger, which can improve the selectivity. In addition, the ratio of the thickness of the second film formed on the surface of the second substrate to the thickness of the first film formed on the surface of the first substrate also becomes higher, which can improve the selectivity.

[0117] In addition, if the first film is made too thick, the H terminal on the surface of the second base is detached and replaced with other terminals in this step, and an inhibitor layer is formed not only on the surface of the first film but also on the surface of the second base in step B, which may hinder the growth of the second film on the surface of the second base in step C. Therefore, the thickness of the first film formed in this step is preferably thinner than the thickness of the second film formed in step C.

[0118] In addition, in this step, it is preferred that the film-forming conditions of the first film be conditions under which the reaction occurs slowly, that is, conditions under which the reactivity and the degree of reaction are reduced, and the H terminals on the surface of the second substrate are retained. In this step, if the film-forming conditions of the first film are set to conditions under which the reactivity and the degree of reaction are high, the H terminals on the surface of the second substrate are separated and replaced with other terminals, and in step B, an inhibitor layer is formed not only on the surface of the first film but also on the surface of the second substrate, and in step C, the growth of the second film on the surface of the second substrate is sometimes hindered. Therefore, in this step, it is preferred that the film-forming conditions of the first film be set to conditions under which the reaction occurs slowly.

[0119] Specifically, for example, by performing this step under at least any one of the following processing conditions, the film forming conditions in this step can be set to conditions where the reaction occurs slowly, and the H terminal on the surface of the second substrate can be retained. In addition, by setting at least any one of the following processing conditions, this step is performed under processing conditions where the film forming rate is lower than that of step C described later.

[0120] The treatment temperature in step A (step A1, step A2) is made higher than the treatment temperature in step C (step C1, step C2).

[0121] The treatment pressure in step A (step A1, step A2) is made lower than the treatment pressure in step C (step C1, step C2).

[0122] The first raw material supply flow rate in step A1 is made smaller than the second raw material supply flow rate in step C1.

[0123] The first oxidant supply flow rate in step A2 is made smaller than the second oxidant supply flow rate in step C2.

[0124] The first raw material supply time in step A1 is made shorter than the second raw material supply time in step C1.

[0125] The first oxidizing agent supply time in step A2 is made shorter than the second oxidizing agent supply time in step C2.

[0126] (Step B)

[0127] Then, by supplying the modifying agent to the wafer 200 , at least a part of the molecular structure of the molecules constituting the modifying agent is adsorbed on the surface of the first film formed on the surface of the first base, thereby forming an inhibitor layer.

[0128] Specifically, valve 243d is opened to allow the modifier to flow into the gas supply pipe 232d. The modifier is flow-regulated by MFC 241d, supplied into the processing chamber 201 through nozzle 249a, and discharged from exhaust port 231a. At this time, the modifier is supplied to the wafer 200 from the side of the wafer 200 (modifier supply). At this time, valves 243e to 243g may also be opened to supply inactive gas into the processing chamber 201 through nozzles 249a to 249c, respectively.

[0129] By supplying the modifier to the wafer 200 under the processing conditions described below, at least a portion of the molecular structure of the molecules constituting the modifier can be selectively (preferentially) adsorbed on the surface of the first film, of the surface of the first film and the surface of the second substrate. Figure 4 As shown in (c), an inhibitor layer is selectively formed on the surface of the first film formed on the surface of the first substrate. That is, in this step, by supplying a modifier to the wafer 200, at least a portion of the molecular structure of the molecules constituting the modifier can be selectively adsorbed on the surface of the first film, thereby modifying the surface of the first film in a manner of forming an inhibitor layer.

[0130] In this step, in order to selectively form an inhibitor layer on the surface of the first film, when the inhibitor layer is formed using a modifier, the property that the incubation time on the surface of the second substrate is longer than the incubation time on the surface of the first film is utilized. As described above, in step A, an oxide film such as a SiO film, a SiOC film, a SiOCN film, etc. is formed on the surface of the first substrate as the first film. The surface of the oxide film includes an OH terminal, and the surface of the Si film as the second substrate includes an H terminal. When forming the inhibitor layer, the incubation time on the H terminal of the surface of the Si film is longer than the incubation time on the OH terminal of the surface of the oxide film. That is, it is difficult to form an inhibitor layer on the surface of the Si film including the H terminal compared to the surface of the oxide film including the OH terminal. Therefore, in this step, the inhibitor layer can be selectively (preferentially) formed on the surface of the oxide film as the first film and the surface of the Si film as the second substrate. In addition, according to such a situation, it can also be said that when it is desired to form an inhibitor layer on a surface including an OH terminal and an H terminal, the H terminal and the surface including the H terminal produce a film formation inhibitory effect (adsorption inhibitory effect, reaction inhibitory effect).

[0131] The inhibitor layer formed in this step contains a residue from the modifier, that is, at least a part of the molecular structure of the molecules constituting the modifier. In the step C described later, the inhibitor layer prevents the second film-forming agent (second raw material) from being adsorbed on the surface of the first film, and hinders (inhibits) the film-forming reaction on the surface of the first film. Therefore, the inhibitor layer is also called a film-forming barrier layer (adsorption barrier layer, reaction barrier layer).

[0132] As at least a part of the molecular structure of the molecule constituting the modifier, for example, trialkylsilyl groups such as trimethylsilyl (-SiMe3) and triethylsilyl (-SiEt3) can be exemplified. In these cases, the surface of the first film is terminated with alkyl groups such as methyl and ethyl. The alkyl groups (alkylsilyl groups) such as methyl (trimethylsilyl) and ethyl (triethylsilyl) that terminate the surface of the first film constitute an inhibitor layer, which can prevent the adsorption of the second film-forming agent (second raw material) on the surface of the first film in the step C described later, thereby hindering (inhibiting) the film-forming reaction on the surface of the first film.

[0133] It should be noted that the term "inhibitor" used in this specification sometimes means a modifier, and sometimes means a residue from a modifier, such as at least a part of the molecular structure of a molecule constituting the modifier, in addition to the film formation inhibitory effect (adsorption inhibitory effect, reaction inhibitory effect), and is sometimes used as a general term for all of these.

[0134] The treatment conditions when supplying the modifying agent in this step are exemplified below.

[0135] Treatment temperature: room temperature (25°C) to 500°C, preferably 25 to 250°C,

[0136] Processing pressure: 5-2000Pa, preferably 10-1000Pa,

[0137] Treatment time: 1 second to 120 minutes, preferably 30 seconds to 60 minutes,

[0138] Modifier supply flow rate: 0.001 to 3 slm, preferably 0.001 to 0.5 slm,

[0139] Inert gas supply flow rate (per gas supply pipe): 0~20slm

[0140] After the inhibitor layer is formed on the surface of the first film, the valve 243d is closed to stop supplying the modifier into the processing chamber 201. Then, according to the same processing process and processing conditions as those of the purging in step A1, the gaseous substances and the like remaining in the processing chamber 201 are removed (purged) from the processing chamber 201. It should be noted that the processing temperature during purging is preferably the same temperature as the processing temperature during supplying the modifier.

[0141] As the modifier, for example, (dimethylamino)trimethylsilane ((CH3)2NSi(CH3)3), (diethylamino)triethylsilane ((C2H5)2NSi(C2H5)3), (dimethylamino)triethylsilane ((CH3)2NSi(C2H5)3), (diethylamino)trimethylsilane ((C2H5)2NSi(CH3)3), (dipropylamino)trimethylsilane ((C3H7)2NSi(CH3)3), (dibutylamino)trimethylsilane ((C3H7)2NSi(CH3)3), (dibutylamino)trimethylsilane ((C3H7)2NSi(CH3)3), (dibutylamino)trimethylsilane ((C3H7)2NSi(CH3)3), (dibutylamino)trimethylsilane ((C3H7)2NSi(CH3)3), (dibutylamino)trimethylsilane ((C3H7)2NSi(CH3)3), (dimethylamino)triethylsilane ((CH3)2NSi(C2H5)3), (diethylamino)trimethylsilane ((C2H5)2NSi(CH3)3), (dipropyl ... As the modifier, one or more of them can be used.

[0142] In addition, as a modifier, for example, bis(dimethylamino)dimethylsilane ([(CH3)2N]2Si(CH3)2), bis(diethylamino)diethylsilane ([(C2H5)2N]2Si(C2H)2), bis(dimethylamino)diethylsilane ([(CH3)2N]2Si(C2H5)2), bis(diethylamino)dimethylsilane ([(C2H5)2N]2Si(CH3)2), bis(dimethylamino)silane ([(CH3)2N]2SiH2), bis(diethylamino)silane ([(C2H5)2N]2SiH2), bis(dimethylaminodimethylsilyl)ethane ([(CH3)2N(CH3)2Si]2C2H6), bis(dipropylamino)silane ([(C3H7)2 N]2SiH2), bis(dibutylamino)silane ([(C4H9)2N]2SiH2), bis(dipropylamino)dimethylsilane ([(C3H7)2N]2Si(CH3)2), bis(dipropylamino)diethylsilane ([(C3H7)2N]2Si(C2H5)2), (dimethylsilyl)diamine ((CH3)2Si(NH2)2), (diethylsilyl)diamine ((C2H5)2Si(NH2)2), (dipropylsilyl)diamine ((C3H7)2Si(NH2)2), bis(dimethylaminodimethylsilyl)methane ([(CH3)2N(CH3)2Si]2CH2), bis(dimethylamino)tetramethyldisilane ([(CH3)2N]2(CH3)4Si2), etc. As the modifier, one or more of them can be used.

[0143] It should be noted that, when implementing this step, at least a part of the molecular structure of the molecules constituting the modifier is sometimes adsorbed on a part of the surface of the second substrate. However, even in this case, the amount of adsorption is very small, and the amount of adsorption on the surface of the first film is overwhelmingly large. In this specification, "selectively (preferentially) adsorbing at least a part of the molecular structure of the molecules constituting the modifier on the surface of the first film" not only includes the case where at least a part of the molecular structure of the molecules constituting the modifier is not adsorbed on the surface of the second substrate at all, and only at least a part of the molecular structure of the molecules constituting the modifier is adsorbed on the surface of the first film, but also includes the case where at least a part of the molecular structure of the molecules constituting the modifier is only very rarely adsorbed on the surface of the second substrate, but at least a part of the molecular structure of the molecules constituting the modifier that is more than that is adsorbed on the surface of the first film.

[0144] (Step C)

[0145] Then, by supplying a second film-forming agent to the wafer 200 on which the inhibitor layer is formed on the surface of the first film, Figure 4As shown in (d), a second film including the first element and the second element is formed on the surface of the second substrate. In this step, specifically, the following steps C1 and C2 are performed in sequence.

[0146] [Step C1]

[0147] In this step, the second raw material and the second catalyst are supplied to the wafer 200. The processing process at this time may be the same as the processing process in step A1.

[0148] By supplying the second raw material and the second catalyst to the wafer 200 under the processing conditions described below, at least a portion of the molecular structure of the molecules constituting the second raw material can be selectively (preferentially) chemically adsorbed on the surface of the second substrate, of the surface of the inhibitor layer and the surface of the second substrate. Thus, a third layer is selectively formed on the surface of the second substrate. The third layer contains a residue from the second raw material, that is, at least a portion of the molecular structure of the molecules constituting the second raw material.

[0149] In this step, in order to selectively form the third layer on the surface of the second substrate, when the second raw material as the second film-forming agent is used to form the third layer, the property that the incubation time on the surface of the inhibitor layer is longer than the incubation time on the surface of the second substrate is utilized. The surface of the Si film as the second substrate contains H terminals as described above, and the surface of the inhibitor layer contains alkyl terminals as described above. When forming the third layer, the incubation time on the alkyl terminals on the surface of the inhibitor layer is longer than the incubation time on the H terminals on the surface of the Si film. That is, it is difficult to form the third layer on the surface of the inhibitor layer containing alkyl terminals compared to the surface of the Si film containing H terminals. Therefore, in this step, the third layer can be selectively (preferentially) formed on the surface of the Si film as the second substrate and the surface of the inhibitor layer. In addition, according to such a situation, it can also be said that when it is desired to form the third layer on the surface containing H terminals and alkyl terminals, the alkyl terminals and the surface containing alkyl terminals produce a film formation inhibition effect (adsorption inhibition effect, reaction inhibition effect).

[0150] The following are examples of treatment conditions when the second raw material and the second catalyst are supplied in this step.

[0151] Treatment temperature: room temperature (25°C) to 200°C, preferably 25 to 150°C,

[0152] Processing pressure: 133-4000Pa, preferably 133-2666Pa,

[0153] Processing time: 1 to 120 seconds, preferably 1 to 90 seconds,

[0154] Second raw material supply flow rate: 0.001 to 3 slm, preferably 0.01 to 2 slm,

[0155] Second catalyst supply flow rate: 0.001 to 3 slm, preferably 0.01 to 2 slm,

[0156] Inert gas supply flow rate (per gas supply pipe): 0~20slm

[0157] After the third layer is formed on the surface of the second substrate, the supply of the second raw material and the second catalyst into the processing chamber 201 is stopped. Then, according to the same processing process and processing conditions as those in the purging in step A1, the gaseous substances and the like remaining in the processing chamber 201 are removed (purged) from the processing chamber 201. It should be noted that the processing temperature during the purging is preferably the same temperature as the processing temperature during the supply of the second raw material and the second catalyst.

[0158] As the second raw material, for example, the same raw materials as the various first raw materials exemplified in the above-mentioned step A1 can be used. The second raw material may be the same substance as the first raw material used in step A1 or may be a different substance, but is preferably the same substance.

[0159] As the second catalyst, for example, the same catalysts as the various first catalysts exemplified in step A1 can be used. The second catalyst may be the same as or different from the first catalyst used in step A1, but is preferably the same.

[0160] [Step C2]

[0161] After step C1 is completed, the second oxidant and the second catalyst are supplied to the wafer 200. The processing process at this time may be the same as the processing process in step A2.

[0162] By supplying the second oxidant and the second catalyst to the wafer 200 under the processing conditions described below, at least a portion of the third layer formed on the surface of the second base in step C1 can be oxidized. Thus, a fourth layer formed by oxidizing the third layer on the surface of the second base is formed.

[0163] The following are examples of treatment conditions when the second oxidizing agent and the second catalyst are supplied in this step.

[0164] Treatment temperature: room temperature (25°C) to 200°C, preferably 25 to 150°C,

[0165] Processing pressure: 133-4000Pa, preferably 133-2666Pa,

[0166] Processing time: 1 to 120 seconds, preferably 1 to 90 seconds,

[0167] Second oxidant supply flow rate: 0.001 to 3 slm, preferably 0.01 to 2 slm,

[0168] Second catalyst supply flow rate: 0.001 to 3 slm, preferably 0.01 to 2 slm,

[0169] Inert gas supply flow rate (per gas supply pipe): 0~20slm

[0170] After the fourth layer is formed on the surface of the second substrate, the supply of the second oxidant and the second catalyst into the processing chamber 201 is stopped. Then, according to the same processing process and processing conditions as those in the purging in step A1, the gaseous substances and the like remaining in the processing chamber 201 are removed (purged) from the processing chamber 201. It should be noted that the processing temperature during the purging is preferably the same temperature as the processing temperature during the supply of the second oxidant and the second catalyst.

[0171] As the second oxidant, for example, the same oxidants as the various first oxidants exemplified in step A2 can be used. The second oxidant may be the same substance as the first oxidant used in step A2 or may be different from the first oxidant, but is preferably the same substance.

[0172] As the second catalyst, for example, the same catalysts as the various first catalysts exemplified in step A1 can be used. The second catalyst may be the same as or different from the first catalyst used in step A1, but is preferably the same.

[0173] [Number of times the regulations are implemented]

[0174] The cycle including the above-mentioned step C1 and step C2, specifically, the cycle of performing step C1 and step C2 non-simultaneously (alternatingly) is performed a predetermined number of times (n times, where n is an integer greater than 1 or 2). Figure 4 As shown in (d), a second film containing the first element and the second element can be selectively formed on the surface of the second substrate of the first substrate and the second substrate of the wafer 200. For example, when the above-mentioned second raw material, the second oxidant and the second catalyst are used, a SiO film, a SiOC film or a SiOCN film as an oxide film can be selectively grown on the surface of the second substrate. In this way, on the surface of the second substrate, for example, a second film in which the first element is Si and the second element is O can also be selectively grown. The first film may also contain C and N.

[0175] It should be noted that the first film and the second film both contain the first element and the second element. The material of the second film may be the same as that of the first film. For example, in the case of the above example, the first film and the second film may both be SiO films, may both be SiOC films, or may both be SiOCN films. It should be noted that the composition ratio (ratio of constituent elements) of the second film may be the same as that of the first film. In addition, the material of the second film may be different from that of the first film. For example, in the case of the above example, the first film may be a SiO film, the second film may be a SiOC film, the first film may be a SiO film, and the second film may be a SiOCN film.

[0176] In other words, the thickness of the fourth layer formed in each cycle is preferably thinner than the desired thickness of the second film, and the above cycle is repeated multiple times until the thickness of the second film formed by stacking the fourth layer reaches the desired thickness.

[0177] It should be noted that, when implementing step C1 and step C2, sometimes the formation and growth of the second film rarely occur on the surface of the inhibitor layer. However, even in this case, the thickness of the second film formed on the surface of the inhibitor layer is much thinner than the thickness of the second film formed on the surface of the second substrate. In this specification, "selectively (preferentially) forming the second film on the surface of the second substrate" not only includes the case where the second film is not formed at all on the surface of the inhibitor layer and the second film is formed only on the surface of the second substrate, but also includes the case where a very thin second film is formed on the surface of the inhibitor layer, but a second film much thicker than the second film is formed on the surface of the second substrate.

[0178] In this step, it is preferred to thicken the thickness of the second film formed on the surface of the second substrate to improve selectivity. The thickness of the second film is preferably, for example, 0.5 nm or more and 15 nm or less. It should be noted that the second film formed in this step is sometimes etched in the same manner as the first film in step D described later. Therefore, it is preferred to thicken the thickness of the second film in advance in this step, taking into account the portion etched in step D.

[0179] (Step D)

[0180] Then, an etchant is supplied to the wafer 200 after the second film is formed on the surface of the second base, thereby removing the first film.

[0181] Specifically, valve 243h is opened to allow etching agent to flow into gas supply pipe 232h. The etching agent is adjusted in flow rate by MFC 241h, supplied into processing chamber 201 through nozzle 249a, and discharged from exhaust port 231a. At this time, etching agent is supplied to wafer 200 from the side of wafer 200 (etching agent supply). At this time, valves 243e to 243g may also be opened to supply inactive gas into processing chamber 201 through nozzles 249a to 249c, respectively.

[0182] By supplying an etchant to the wafer 200 under the processing conditions described below, the first film formed on the surface of the first substrate can be removed (etched) to expose the surface of the first substrate. It should be noted that when the first film is removed, the inhibitor layer remaining on the surface of the first film is also removed. Figure 4 As shown in (e), the surface of the first base of the wafer 200 is exposed.

[0183] The following are examples of processing conditions when the etching agent is supplied in this step.

[0184] Treatment temperature: room temperature (25°C) to 400°C, preferably 50 to 200°C,

[0185] Processing pressure: 1-13332 Pa, preferably 100-1333 Pa,

[0186] Treatment time: 0.1 to 60 minutes, preferably 1 to 30 minutes,

[0187] Etching agent supply flow rate: 0.05 to 5 slm, preferably 0.1 to 2 slm,

[0188] Inert gas supply flow rate (per gas supply pipe): 1 to 10 slm, preferably 2 to 10 slm.

[0189] After the first film on the surface of the first substrate is removed, the valve 243h is closed to stop the supply of the etchant into the processing chamber 201. Then, according to the same processing process and processing conditions as those in the purging in step A1, the gaseous substances and the like remaining in the processing chamber 201 are removed (purged) from the processing chamber 201. In addition, the processing temperature during the purging is preferably the same temperature as the processing temperature during the supply of the etchant.

[0190] As an etchant, for example, a fluorine (F)-containing substance (F-containing gas) can be used. As an etchant, for example, a fluorine (F)-containing substance (F-containing gas) such as chlorine trifluoride (ClF3), chlorine fluoride (ClF), nitrogen fluoride (NF3), fluorine (F2), hydrogen fluoride (HF), HF aqueous solution (DHF) can be used. As an etchant, one or more of them can be used.

[0191] (Post-purge and atmospheric pressure recovery)

[0192] After step D is completed, inert gas is supplied from nozzles 249a to 249c as purge gas into the processing chamber 201, and the gas is exhausted from the exhaust port 231a. Thus, the processing chamber 201 is purged, and the gas, reaction by-products, etc. remaining in the processing chamber 201 are removed from the processing chamber 201 (post-purge). After that, the atmosphere in the processing chamber 201 is replaced with inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure restoration).

[0193] (Cassette unloading and wafer release)

[0194] After that, the sealing cover 219 is lowered by the wafer box elevator 115 to open the lower end of the manifold 209. Then, the processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the wafer box 217 (wafer box unloading). After the wafer box is unloaded, the baffle 219s moves, and the lower end opening of the manifold 209 is sealed by the baffle 219s via the O-ring 220c (baffle closing). After the processed wafer 200 is carried out to the outside of the reaction tube 203, it is taken out from the wafer box 217 (wafer release).

[0195] (3) Effects of this method

[0196] According to this aspect, one or more of the following effects can be obtained.

[0197] By carrying out step A, step B, step C, the second film can be selectively formed on the surface of the second substrate with high precision. This is because the incubation time on the surface of the second substrate is longer than the incubation time on each surface of the first substrate and the first film, and the incubation time on the surface of the inhibitor layer is longer than the incubation time on the surface of the second substrate. That is, this is because the incubation time on the surface of the inhibitor layer is the longest, the incubation time on the surface of the second substrate is the second longest, and the incubation time on each surface of the first substrate and the first film is the shortest. In this way, by controlling the balance of the incubation time on each surface, in step A, the first film can be selectively formed on the surface of the first substrate, in step B, the inhibitor layer can be selectively formed on the surface of the first film, and in step C, the second film can be selectively formed on the surface of the second substrate with high precision. That is, according to this mode, a desired film can be selectively formed on a desired surface with high precision.

[0198] By performing step A, step B, and step C, a first film containing the first element and the second element is formed on the surface of the first substrate, an inhibitor layer is formed on the surface of the first film, and a second film containing the first element and the second element is formed on the surface of the second substrate. For example, when the first film contains the first element and the second element, and the second film contains the third element and the fourth element, there is a possibility that the third element and the fourth element are mixed into the first film, and the first element and the second element are mixed into the second film, that is, the possibility of cross contamination, and the film properties may be reduced. In contrast, by the first film and the second film containing the same element, namely the first element and the second element, respectively, the above-mentioned cross contamination can be prevented, and the film properties can be improved. In particular, when the first film and the second film are formed in the same processing chamber (in situ), the effect is remarkable.

[0199] In addition, by making the first film and the second film contain the first element and the second element respectively, when the first film is etched back by an etchant after the second film is formed, that is, when step D is performed after step C, the film thickness of the second film exposed to the etchant together with the first film can be controlled with high controllability. In addition, by making the first film and the second film contain the first element and the second element respectively, the supply system of the first film-forming agent used to form the first film and the supply system of the second film-forming agent used to form the second film can be shared, and the supply system can be simplified. As a result, the cost of the device can be greatly reduced and the maintenance of the device can be simplified. In addition, by making the first film and the second film contain the first element and the second element respectively, the film forming temperature of the first film can be equal to the film forming temperature of the second film, and when the processing of steps A, B, and C is repeatedly performed on different wafers 200, that is, when different wafers 200 are continuously processed, the yield can be improved, and the productivity in the continuous processing can be improved.

[0200] It should be noted that the first film is preferably an oxide film and the second film is an oxide film, and it is more preferred that the first element is Si and the second element is O. It is particularly preferred that the first film is a SiO film, a SiOC film or a SiOCN film, and the second film is a SiO film, a SiOC film or a SiOCN film. Thus, the above-mentioned effect can be effectively produced. It should be noted that the materials (molecular structure, constituent elements) of the two films can be the same as in the case where both the first film and the second film are set as SiO films. In this case, when step D is performed after step C, the second film is etched in the same way as the first film, so the film thickness of the second film can be controlled with higher controllability. In addition, the materials of the two films can be different, as in the case where the first film is set as a SiO film and the second film is set as a SiOC film or a SiOCN film. In this case, by setting the first film as a SiO film and the second film as a SiOC film or a SiOCN film, when step D is performed after step C, the etching of the second film can be suppressed by the effect of the second film containing C and N, and the first film can be selectively etched. Thus, when etching the first film, the film thickness of the second film exposed to the etchant together with the first film can be controlled with higher controllability.

[0201] Preferably, in step A, a first raw material and a first oxidant are supplied to the wafer 200 as a first film-forming agent, and in step C, a second raw material and a second oxidant are supplied to the wafer 200 as a second film-forming agent. Specifically, preferably, in step A, a cycle including step A1 of supplying the first raw material to the wafer 200 and step A2 of supplying the first oxidant to the wafer 200 is performed a predetermined number of times, and in step C, a cycle including step C1 of supplying the second raw material to the wafer 200 and step C2 of supplying the second oxidant to the wafer 200 is performed a predetermined number of times. Preferably, in at least any one of step A1 and step A2, a first catalyst is further supplied, and in at least any one of step C1 and step C2, a second catalyst is further supplied. Thus, the above-mentioned effect can be effectively produced. In addition, through the action of each catalyst, the processing temperature in each step can be reduced, the reaction occurring in each step can be softened, and the selectivity in the selective growth of the first film and the second film can be improved.

[0202] The first raw material and the second raw material are substances containing at least any one of an amino group, an alkoxy group and a chloro group, and the first oxidant and the second oxidant are preferably substances containing O and H. It should be noted that the first raw material and the second raw material may be the same substance or different substances. In addition, the first oxidant and the second oxidant may be the same substance or different substances. It should be noted that it is more preferred that the first raw material and the second raw material are the same substance, and the first oxidant and the second oxidant are the same substance. In addition, when the first catalyst and the second catalyst are used, it is more preferred that the first raw material and the second raw material are the same substance, the first oxidant and the second oxidant are the same substance, and the first catalyst and the second catalyst are the same substance. These can also be said to be the case where the first film-forming agent and the second film-forming agent are the same substance. Thus, the above-mentioned effect can be effectively produced.

[0203] It is preferred that the thickness of the first film is less than the thickness of the second film, or that the thickness of the first film is thinner than that of the second film. In addition, it is preferred that step A be performed under a processing condition where the film formation rate is lower than that of step C. Thus, the reaction when forming the first film can be made gentler than the reaction when forming the second film, the ratio of the thickness of the second film formed on the surface of the second substrate to the thickness of the first film formed on the surface of the first substrate can be increased, and the selectivity can be improved.

[0204] It is preferable that the temperature of the wafer 200 is the same in step A, step B, and step C. That is, it is preferable that the processing temperature is the same in step A, step B, and step C. Thereby, the above-mentioned effect related to productivity can be effectively produced.

[0205] In addition, it is preferred to perform step A, step B, and step C in the same space. That is, as described above, it is preferred to perform step A, step B, and step C in the same processing chamber (in situ). Thus, step A, step B, and step C can be performed continuously without sandwiching the process of transporting the wafer 200 between them. Thus, the output rate can be improved, and the productivity can be improved. Furthermore, by performing step A, step B, and step C in the same space (in the same processing chamber), it is possible to prevent the wafer 200 from being exposed to the atmosphere between the steps, and undesirable conditions such as selectivity deterioration caused by exposure to the atmosphere can be prevented, and selective growth can be appropriately performed. In addition, as described above, in addition to step A, step B, and step C, it is also preferred to further perform step D in the same space (in the same processing chamber).

[0206] (4) Modification

[0207] The processing flow in this embodiment can be changed as shown in the following modified examples. These modified examples can be combined arbitrarily. Unless otherwise specified, the processing process and processing conditions in each step of each modified example can be set to be the same as the processing process and processing conditions in each step of the above-mentioned processing flow.

[0208] (Variant 1)

[0209] When it is not necessary to remove the first film formed on the surface of the first base as in the following process flow, step D can be omitted. In this modification, the same effects as those of the above-described embodiment can be obtained.

[0210] (first raw material + first catalyst → first oxidant + first catalyst) × m → modifier → (second raw material + second catalyst → second oxidant + second catalyst) × n

[0211] (Variant 2)

[0212] (e) Step E of forming a third film on the second film may also be performed by supplying a third film-forming agent to the wafer 200 after the second film is formed. Step E is preferably performed after step C and before step D. In the following example, a case where a third raw material, a third oxidant, and a third catalyst are supplied to the wafer 200 as the third film-forming agent in step E is described. In this case, in step E, it is preferred that a cycle including step E1 (e1) supplying a third raw material and a third catalyst to the wafer 200 and step E2 (e2) supplying a third oxidant and a third catalyst to the wafer 200 is performed a predetermined number of times (p times, where p is an integer greater than 1 or 2) as in the process flow shown below. It should be noted that the supply of the third catalyst may be omitted in at least one of step E1 and step E2.

[0213] (first raw material + first catalyst → first oxidant + first catalyst) × m → modifier → (second raw material + second catalyst → second oxidant + second catalyst) × n → (third raw material + third catalyst → third oxidant + third catalyst) × p → etchant (etch back)

[0214] Main reference Figure 5 (a)~ Figure 5 (f) This modification example is described. First, similarly to the above method, use Figure 5 (a) shows a wafer 200 having a first substrate and a second substrate on the surface. The wafer 200 is used to perform step A, as shown in FIG. Figure 5 (b), selectively forming a first film on the surface of the first substrate. Then, step B is performed, as shown in Figure 5 (c) shows that an inhibitor layer is formed on the surface of the first film. Then, step C is performed, as shown in Figure 5 (d), a second film is selectively formed on the surface of the second substrate. Then, step E is performed, as shown in Figure 5 (e), a third film is selectively formed on the surface of the second film. Then, step D is performed, as shown in Figure 5 As shown in (f), the first film formed on the surface of the first substrate is removed together with the inhibitor layer. In this way, a stacked film formed by stacking the second film and the third film is selectively formed on the surface of the second substrate of the first substrate and the second substrate of the wafer 200.

[0215] The processing process and processing conditions of step E in this variant example can be set to be the same as the processing process and processing conditions of step C in the above-mentioned processing flow, except that a third film-forming agent (third raw material, third oxidant, third catalyst) is used and the object to which the third film-forming agent is supplied is the wafer 200 after step C. As the third raw material, for example, the same raw material as the various first raw materials exemplified in the above-mentioned step A1 can be used. As the third oxidant, for example, the same oxidant as the various first oxidants exemplified in the above-mentioned step A2 can be used. The third catalyst can use the same catalyst as the various first catalysts exemplified in the above-mentioned step A1. It should be noted that the third film-forming agent (third raw material, third oxidant, third catalyst) is preferably a substance different from the second film-forming agent (second raw material, second oxidant, second catalyst). In addition, the third film is preferably a material different from the second film. In addition, the third film is preferably a material different from the first film. For example, when the first film is set as a SiO film and the second film is set as a SiO film, the third film can be set as a SiOC film or a SiOCN film. Furthermore, for example, when the first film is a SiO film and the second film is a SiOC film, the third film can be a SiOC film or a SiOCN film.

[0216] In this variant, the same effect as the above-mentioned method can also be obtained. In addition, in this variant, by forming a third film on the second film, when the first film is etched back by an etchant after the second film is formed, the third film can be made to function as an etching barrier film (cap film, etching barrier film, etching inhibitor film). Therefore, it is preferred to set the third film to a film having higher etching resistance than the second film. In addition, it is preferred to set the third film to a film having higher etching resistance than the first film. For example, by setting the third film to a film containing C and N such as a SiOC film or a SiOCN film, the third film can be made to be a film with high etching resistance. Thus, the first film can be selectively etched without etching the second film, and even when the first film is etched back, the film thickness of the second film can be controlled with high controllability.

[0217] <Other aspects of the present disclosure>

[0218] The embodiments of the present disclosure have been specifically described above. However, the present disclosure is not limited to the above embodiments, and various modifications can be made without departing from the gist of the present disclosure.

[0219] For example, the wafer 200 may have a plurality of regions of different materials as the first substrate, or may have a plurality of regions of different materials as the second substrate. In the wafer 200, if it is a substrate including a surface (end) whose incubation time when forming the first film is shorter than that of the second substrate, any substrate can be used as the first substrate. That is, in the wafer 200, if it is a substrate including at least two surfaces with a difference in incubation time when forming the first film, it can be used as the first substrate and the second substrate. For example, it is preferred that the first substrate includes an insulating film, and the second substrate includes at least one of a semiconductor substrate, a semiconductor element single film, and a metal element single film. The insulating film preferably includes at least one of a semiconductor insulating film and a metal insulating film. In these cases, when forming the first film, the above-mentioned difference in incubation time can be appropriately generated on each surface of the first substrate and the second substrate. In this method, the same effect as the above method can also be obtained.

[0220] In addition to the above-mentioned SiN film, the first substrate may also be a SiO film (including a natural oxide film), a SiOC film, a SiOCN film, a silicon oxynitride film (SiON film), a silicon carbide film (SiC film), a silicon carbonitride film (SiCN film), a silicon boron nitride film (SiBN film), a silicon boron carbonitride film (SiBCN film), other Si-based insulating films and other semiconductor insulating films, a hafnium oxide film (HfO film), a zirconium oxide film (ZrO film), an aluminum oxide film (AlO film), other metal-based oxide films and other metal insulating films. At least any one of these can be used as the first substrate.

[0221] In addition to the above-mentioned Si film, the second substrate may also be a semiconductor substrate such as a Si wafer (single crystal Si). It should be noted that the Si film includes semiconductor element single films such as amorphous silicon film (a-Si film), polycrystalline silicon film (poly-Si film), mixed crystal film of amorphous silicon and polycrystalline silicon, epitaxial silicon film (Epi-Si film). In addition, the second substrate may also be a metal element single film such as a copper film (Cu film), a tungsten film (W film), a ruthenium film (Ru film), a cobalt film (Co film), a molybdenum film (Mo film). As the second substrate, at least any one of them can be used.

[0222] In addition, in the above-mentioned manner, an example of performing the above-mentioned process flow in the same processing chamber of the same processing device (in-situ) is described. The present disclosure is not limited to the above-mentioned manner. For example, any step of the above-mentioned process flow and other arbitrary steps can be performed in different processing chambers of different processing devices (non-in-situ), or can be performed in different processing chambers of the same processing device. In these cases, the same effect as in the above-mentioned manner can also be obtained.

[0223] In the above-mentioned cases, if a series of steps are performed in situ, the wafer 200 will not be exposed to the atmosphere during the process, and the wafer 200 can be processed consistently while being placed in a vacuum state, so that stable processing can be performed. In addition, if a part of the steps are performed ex situ, the temperature in each processing chamber can be pre-set to, for example, the processing temperature in each step or a temperature close thereto, which can shorten the time required for temperature adjustment and improve the yield, that is, productivity.

[0224] The recipe used in each treatment is preferably prepared separately according to the treatment content, and is recorded and stored in the storage device 121c via a telecommunication line or an external storage device 123. Moreover, when starting each treatment, it is preferred that the CPU 121a appropriately selects an appropriate recipe from a plurality of recipes recorded and stored in the storage device 121c according to the treatment content. Thus, films of various film types, composition ratios, film qualities, and film thicknesses can be formed with good reproducibility in the treatment device. In addition, the burden on the operator can be reduced, operational errors can be avoided, and each treatment can be started quickly.

[0225] The above-mentioned formula is not limited to the case of newly making, and can also be prepared by, for example, changing an existing formula already installed in a processing device. When changing the formula, the changed formula can also be installed in the processing device via a telecommunication line or a recording medium recording the formula. In addition, the input / output device 122 of the existing processing device can be operated to directly change the existing formula already installed in the processing device.

[0226] In the above-mentioned method, an example of forming a film using a batch-type processing device that processes multiple substrates at a time is described. The present disclosure is not limited to the above-mentioned method, for example, when a film is formed using a single-chip processing device that processes one or more substrates at a time, it can also be appropriately applied. In addition, in the above-mentioned method, an example of forming a film using a processing device having a hot-wall type processing furnace is described. The present disclosure is not limited to the above-mentioned method, and when a film is formed using a processing device having a cold-wall type processing furnace, it can also be appropriately applied.

[0227] When using these processing devices, each treatment can be performed by the same processing process and processing conditions as the above-mentioned methods and modified examples, and the same effect as the above-mentioned methods and modified examples can be obtained. The above-mentioned methods and modified examples can be used in appropriate combinations. At this time, the processing process and processing conditions can be set to be the same as the processing process and processing conditions of the above-mentioned methods and modified examples.

Claims

1. A processing method, comprising: (a) supplying a first film-forming agent to a substrate having a first base and a second base on a surface thereof, thereby forming a first film containing a first element and a second element on a surface of the first base, (b) supplying a modifying agent to the substrate so that at least a part of the molecular structure of the molecules constituting the modifying agent is adsorbed on the surface of the first film formed on the surface of the first base to form an inhibitor layer, and (c) forming a second film containing the first element and the second element on the surface of the second base by supplying a second film-forming agent to the substrate having the inhibitor layer formed on the surface of the first film.

2. The processing method according to claim 1, wherein: The first film is an oxide film, and the second film is an oxide film.

3. The processing method according to claim 1, wherein: The first element is silicon, and the second element is oxygen.

4. The processing method according to claim 3, wherein: The first film is a silicon oxide film, a silicon oxycarbon film, or a silicon oxynitride and carbon film, and the second film is a silicon oxide film, a silicon oxycarbon film, or a silicon oxynitride and carbon film.

5. The processing method according to claim 1, wherein: The material of the first film is the same as that of the second film.

6. The processing method according to claim 1, wherein: In (a), a first raw material and a first oxidizing agent are supplied to the substrate as the first film-forming agent. In (c), a second raw material and a second oxidizing agent are supplied to the substrate as the second film-forming agent.

7. The processing method according to claim 6, wherein: In (a), a cycle including (a1) supplying the first raw material to the substrate and (a2) supplying the first oxidizing agent to the substrate is performed a predetermined number of times, In (c), a cycle including the step of (c1) supplying the second raw material to the substrate and the step of (c2) supplying the second oxidizing agent to the substrate is performed a predetermined number of times.

8. The processing method according to claim 7, wherein: In at least one of (a1) and (a2), a first catalyst is further supplied, In at least any one of (c1) and (c2), a second catalyst is further supplied.

9. The processing method according to any one of claims 6 to 8, wherein: The first raw material and the second raw material are substances containing at least any one of an amino group, an alkoxy group, and a chloro group, The first oxidant and the second oxidant are substances containing oxygen and hydrogen.

10. The processing method according to any one of claims 6 to 8, wherein: The first raw material and the second raw material are the same substance, The first oxidant and the second oxidant are the same substance.

11. The processing method according to claim 8, wherein: The first raw material and the second raw material are the same substance, The first oxidant and the second oxidant are the same substance, The first catalyst and the second catalyst are the same material.

12. The processing method according to any one of claims 1 to 5, wherein: The thickness of the first film is set to be less than or equal to the thickness of the second film, or the thickness of the first film is set to be thinner than the thickness of the second film.

13. The processing method according to any one of claims 1 to 5, wherein: (a) is carried out under processing conditions where the film formation rate is lower than that of (c).

14. The processing method according to any one of claims 1 to 5, wherein: The temperature of the substrate in (a), (b) and (c) is made the same.

15. The processing method according to any one of claims 1 to 5, wherein: Carry out (a), (b) and (c) in the same space.

16. The processing method according to any one of claims 1 to 5, wherein: It also has the following processes: (d) After the second film is formed on the surface of the second base, the first film is removed by supplying an etchant to the substrate.

17. The processing method according to any one of claims 1 to 5, wherein: It also has the following processes: (e) supplying a third film-forming agent to the substrate on which the second film is formed, thereby forming a third film on the second film.

18. The processing method according to any one of claims 1 to 5, wherein: The first substrate includes an insulating film, The second base includes at least any one of a semiconductor substrate, a semiconductor element single substance film, and a metal element single substance film.

19. A method for manufacturing a semiconductor device, comprising: (a) supplying a first film-forming agent to a substrate having a first base and a second base on a surface thereof, thereby forming a first film containing a first element and a second element on a surface of the first base, (b) supplying a modifying agent to the substrate so that at least a part of the molecular structure of the molecules constituting the modifying agent is adsorbed on the surface of the first film formed on the surface of the first base to form an inhibitor layer, and (c) forming a second film containing the first element and the second element on the surface of the second base by supplying a second film-forming agent to the substrate having the inhibitor layer formed on the surface of the first film.

20. A processing device comprising: A first film-forming agent supply system supplies the first film-forming agent to the substrate, Modifier supply system supplies modifier to the substrate. a second film-forming agent supply system for supplying the second film-forming agent to the substrate, and A control unit configured to control the first film-forming agent supply system, the modifier supply system, and the second film-forming agent supply system to perform the following processing: (a) a process of forming a first film containing a first element and a second element on a surface of the first substrate by supplying the first film-forming agent to a substrate having a first substrate and a second substrate on a surface thereof, (b) supplying the modifying agent to the substrate to cause at least a portion of the molecular structure of the molecules constituting the modifying agent to adsorb to the surface of the first film formed on the surface of the first base to form an inhibitor layer, and (c) A process of forming a second film containing the first element and the second element on the surface of the second base by supplying the second film-forming agent to the substrate having the inhibitor layer formed on the surface of the first film.

21. A computer-readable recording medium having a program recorded thereon, wherein the program causes a processing device to execute the following process via a computer: (a) supplying a first film-forming agent to a substrate having a first base and a second base on a surface thereof, thereby forming a first film containing a first element and a second element on a surface of the first base, (b) supplying a modifier to the substrate so that at least a part of the molecular structure of the molecules constituting the modifier is adsorbed on the surface of the first film formed on the surface of the first base to form an inhibitor layer, and (c) forming a second film containing the first element and the second element on the surface of the second base by supplying a second film-forming agent to the substrate having the inhibitor layer formed on the surface of the first film.

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