Processing method, manufacturing method of semiconductor device, processing device, and program

Abstract

To provide a technique for selectively forming a film on a desired surface with high accuracy.SOLUTION: A processing method includes steps of: (a) supplying a first deposition agent to a substrate including a first base and a second base on a surface, 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, thereby forming an inhibitor layer by adsorbing at least a part of a molecular structure of molecules constituting the modifier onto a surface of the first film formed on the surface of the first base; and (c) supplying a second deposition agent to the substrate where the inhibitor layer is formed on the surface of the first film, thereby forming a second film containing the first element and the second element on a surface of the second base.SELECTED DRAWING: Figure 4

Description

[Technical field]

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

[0002] As one step in the manufacturing process of a semiconductor device, a process may be performed in which a film is selectively grown and formed on a specific surface among multiple types of surfaces made of different materials exposed on the surface of a substrate (hereinafter, this process is also referred to as selective growth or selective film formation) (see, for example, Patent Documents 1 to 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-106242 [Patent Document 2] JP 2020-155452 A [Patent Document 3] JP 2020-155607 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a technique for selectively forming a film on a desired surface with high precision. [Means for solving the problem]

[0005] According to one aspect of the present disclosure, (a) supplying a first film-forming agent to a substrate having a first underlayer and a second underlayer on a surface thereof to form a first film containing a first element and a second element on a surface of the first underlayer; (b) supplying a modifier to the substrate to adsorb at least a part of a molecular structure of a molecule constituting the modifier onto the surface of the first film formed on the surface of the first base, thereby forming an inhibitor layer; (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; The present invention provides a technique having the following features: Effect of the Invention

[0006] According to the present disclosure, it becomes possible to selectively form a film on a desired surface with high precision. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a processing apparatus suitably used in one embodiment of the present disclosure, showing a processing furnace 202 portion in vertical cross section. [Diagram 2] FIG. 2 is a schematic diagram of a vertical processing furnace of a processing apparatus preferably used in one embodiment of the present disclosure, showing a processing furnace 202 portion in a cross-sectional view taken along line AA in FIG. [Diagram 3] FIG. 3 is a schematic configuration diagram of a controller 121 of a processing apparatus preferably used in one embodiment of the present disclosure, and is a block diagram showing a control system of the controller 121. [Figure 4] FIG. 4(a) is a schematic cross-sectional view showing a surface portion of a wafer having a first underlayer and a second underlayer on its surface. FIG. 4(b) is a schematic cross-sectional view showing a surface portion of a wafer after selectively forming a first film on the surface of the first underlayer by performing step A from the state of FIG. 4(a). FIG. 4(c) is a schematic cross-sectional view showing a surface portion of a wafer after selectively forming an inhibitor layer on the surface of the first film formed on the surface of the first underlayer by performing step B from the state of FIG. 4(b). FIG. 4(d) is a schematic cross-sectional view showing a surface portion of a wafer after selectively forming a second film on the surface of the second underlayer by performing step C from the state of FIG. 4(c). FIG. 4(e) is a schematic cross-sectional view showing a surface portion of a wafer after selectively removing the first film formed on the surface of the first underlayer together with the inhibitor layer by performing step D from the state of FIG. 4(d). [Diagram 5]Figures 5(a) to 5(d) are similar to Figures 4(a) to 4(d), respectively. Figure 5(e) is a schematic cross-sectional view showing a surface portion of a wafer after selectively forming a third film on the surface of the second film formed on the surface of the second base by performing step E from the state of Figure 5(d). Figure 5(f) is a schematic cross-sectional view showing a surface portion of a wafer after removing the first film formed on the surface of the first base together with the inhibitor layer by performing step D from the state of Figure 5(e). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] <One aspect of the present disclosure> Hereinafter, one embodiment of the present disclosure will be described mainly with reference to Figures 1 to 3 and 4(a) to 4(e). Note that the drawings used in the following description are all schematic, and the dimensional relationships of the elements, the ratios of the elements, etc. shown in the drawings do not necessarily match the actual ones. Furthermore, the dimensional relationships of the elements, the ratios of the elements, etc. between multiple drawings do not necessarily match.

[0009] (1) Configuration of processing device (processing system) As shown in Fig. 1, the processing furnace 202 of the processing apparatus has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is installed vertically by being supported by a holding plate. The heater 207 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.

[0010] A reaction tube 203 is disposed inside the heater 207 concentrically with the heater 207. The reaction tube 203 is made of, for example, quartz (SiO 2The reaction tube 203 is made of a heat-resistant material such as SUS or silicon carbide (SiC) and is formed in a cylindrical shape with the upper end closed and the lower end open. A manifold 209 is disposed concentrically with the reaction tube 203 below the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS) and is formed in a cylindrical shape with the upper and lower ends open. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a is provided as a seal member between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically like the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in the cylindrical hollow part of the processing vessel. The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate. In the processing chamber 201, processing of the wafer 200 is performed.

[0011] Nozzles 249a to 249c serving as first to third supply units are provided in the processing chamber 201 so as to penetrate the sidewall of the manifold 209, respectively. The nozzles 249a to 249c are also referred to as first to third nozzles, respectively. The nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC. Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively. The nozzles 249a to 249c are different nozzles, and each of the nozzles 249a and 249c is provided adjacent to the nozzle 249b.

[0012] Gas supply pipes 232a-232c are provided with mass flow controllers (MFCs) 241a-241c, which are flow rate controllers (flow rate control parts), and valves 243a-243c, which are on-off valves, in order from the upstream side of the gas flow. Gas supply pipes 232d, 232e, and 232h are connected to the downstream side of valve 243a of gas supply pipe 232a. Gas supply pipes 232f and 232g are connected to the downstream sides of valves 243b and 243c of gas supply pipes 232b and 232c. Gas supply pipes 232d-232h are provided with MFCs 241d-241h and valves 243d-243h in order from the upstream side of the gas flow. Gas supply pipes 232a-232h are made of a metal material, such as SUS.

[0013] As shown in FIG. 2, the nozzles 249a to 249c are provided in a circular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, from the lower part to the upper part of the inner wall of the reaction tube 203, so as to rise upward in the arrangement direction of the wafers 200. That is, the nozzles 249a to 249c are provided in a region horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region in which the wafers 200 are arranged, so as to extend along the wafer arrangement region. In a plan view, the nozzle 249b is disposed so as to face an exhaust port 231a (described later) on a straight line across the center of the wafer 200 loaded into the processing chamber 201. The nozzles 249a and 249c are disposed so as to sandwich a straight line L passing through the nozzle 249b and the center of the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer periphery of the wafer 200). The straight line L is also a straight line passing through the nozzle 249b and the center of the wafer 200. In other words, the nozzle 249c is provided on the opposite side of the nozzle 249a across the line L. The nozzles 249a and 249c are arranged symmetrically with respect to the line L. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. The gas supply holes 250a to 250c are each opened to face (face) the exhaust port 231a in a plan view, and are capable of supplying gas toward the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203.

[0014] From the gas supply pipe 232a, raw materials, that is, a first raw material, a second raw material, and a third raw material are supplied into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a. 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.

[0015] From the gas supply pipe 232b, catalysts, i.e., a first catalyst, a second catalyst, and a third catalyst, are supplied into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b. 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.

[0016] From the gas supply pipe 232c, oxidizers, i.e., a first oxidizer, a second oxidizer, and a third oxidizer, are supplied into the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c. The first oxidizer is used as one of the first film forming agents. The second oxidizer is used as one of the second film forming agents. The third oxidizer is used as one of the third film forming agents.

[0017] The modifying agent is supplied from the gas supply pipe 232d into the processing chamber 201 via the MFC 241d, the valve 243d, the gas supply pipe 232a, and the nozzle 249a.

[0018] An etching agent is supplied from the gas supply pipe 232h into the processing chamber 201 via the MFC 241h, the valve 243h, the gas supply pipe 232a, and the nozzle 249a.

[0019] From the gas supply pipes 232e to 232g, an inert gas is supplied via the MFCs 241e to 241g, the valves 243e to 243g, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c, respectively, into the processing chamber 201. The inert gas acts as a purge gas, a carrier gas, a dilution gas, or the like.

[0020] A raw material supply system (first raw material supply system, second raw material supply system, third raw material supply system) is mainly constituted by the gas supply pipe 232a, the MFC 241a, and the valve 243a. A catalyst supply system (first catalyst supply system, second catalyst supply system, third catalyst supply system) is mainly constituted by the gas supply pipe 232b, the MFC 241b, and the valve 243b. An oxidant supply system (first oxidant supply system, second oxidant supply system, third oxidant supply system) is mainly constituted by the gas supply pipe 232c, the MFC 241c, and the valve 243c. The raw material supply system (first raw material supply system, second raw material supply system, third raw material supply system), catalyst supply system (first catalyst supply system, second catalyst supply system, third catalyst supply system), and oxidizing agent supply system (first oxidizing agent supply system, second oxidizing agent supply system, third oxidizing agent supply system) are also referred to as film forming agent supply system (first film forming agent supply system, second film forming agent supply system, third film forming agent supply system). The gas supply pipe 232d, MFC 241d, and valve 243d mainly constitute a modifying agent supply system. The gas supply pipe 232h, MFC 241h, and valve 243h mainly constitute an etching agent supply system. The gas supply pipes 232e to 232g, MFCs 241e to 241g, and valves 243e to 243g mainly constitute an inert gas supply system.

[0021] Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which the valves 243a-243h, the MFCs 241a-241h, etc. are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a-232h, and is configured so that the supply operation of various substances (various gases) into the gas supply pipes 232a-232h, that is, the opening and closing operation of the valves 243a-243h and the flow rate adjustment operation by the MFCs 241a-241h, etc., are controlled by a controller 121 described later. The integrated supply system 248 is configured as an integrated or split type integrated unit, and can be attached and detached to and from the gas supply pipes 232a-232h, etc., in units of integrated units, and is configured so that maintenance, replacement, expansion, etc. of the integrated supply system 248 can be performed in units of integrated units.

[0022] An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided at the lower side of the side wall of the reaction tube 203. As shown in FIG. 2, the exhaust port 231a is provided at a position facing the nozzles 249a to 249c (gas supply holes 250a to 250c) across the wafer 200 in a plan view. The exhaust port 231a may be provided along the side wall of the reaction tube 203 from the lower part to the upper part, that is, along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit). The APC valve 244 is configured to be able to evacuate and stop the evacuation of the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating, and further configured to be able to adjust the pressure inside the processing chamber 201 by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating. An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

[0023] Below the manifold 209, a seal cap 219 is provided as a furnace port cover body capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal material such as SUS, and is formed in a disk shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a seal member that abuts against the lower end of the manifold 209. Below the seal cap 219, a rotation mechanism 267 is provided for rotating the boat 217, which will be described later. A rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217 through the seal cap 219. The rotation mechanism 267 is configured to rotate the wafers 200 by rotating the boat 217. The seal cap 219 is configured to be vertically raised and lowered by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers the wafers 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219.

[0024] A shutter 219s is provided below the manifold 209 as a furnace port cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is carried out of the processing chamber 201. The shutter 219s is made of a metal material such as SUS and is formed in a disk shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a seal member that comes into contact with the lower end of the manifold 209. The opening and closing operation (lifting and lowering operation, rotating operation, etc.) of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

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

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

[0027] As shown in FIG. 3, the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122 configured as, for example, a touch panel is connected to the controller 121. An external storage device 123 can be connected to the controller 121. The processing device may be configured to include one control unit or multiple control units. That is, the control for performing the processing sequence described later may be performed using one control unit or multiple control units. The multiple control units may be configured as a control system connected to each other by a wired or wireless communication network, and the control for performing the processing sequence described later may be performed by the entire control system. In this specification, when the term "control section" is used, it may include one control section, or may include multiple control sections, or may include a control system made up of multiple control sections.

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

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

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

[0031] The controller 121 can be configured by installing the above-mentioned program recorded and stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, and a semiconductor memory such as a USB memory or an SSD. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media. When the term recording media is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both of them. The program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0032] (2) Treatment process An example of a method of 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, a processing sequence for selectively forming a film on the surface of the second underlayer of the first and second underlayers on the surface of a wafer 200 as a substrate, will be described mainly with reference to Figs. 4(a) to 4(e). In the following description, the operation of each part constituting the processing apparatus is controlled by a controller 121. The processing apparatus will also be referred to as a substrate processing apparatus, a film formation processing apparatus, or a film formation apparatus. The processing method will also be referred to as a substrate processing method, a film formation processing method, or a film formation method.

[0033] As shown in Fig. 4(a), the wafer 200 as a substrate has a first underlayer and a second underlayer on its surface. In the following description, for convenience, a typical example will be described in which the first underlayer is a silicon nitride film (SiN film) and the second underlayer is a silicon film (Si film).

[0034] In the processing sequence of this embodiment, (a) Step A of supplying a first film forming agent to a wafer 200 having a first underlayer and a second underlayer on a surface thereof to form a first film including a first element and a second element on the surface of the first underlayer; (b) Step B of supplying a modifier to the wafer 200 to adsorb at least a part of the molecular structure of the molecules constituting the modifier onto the surface of the first film formed on the surface of the first base, thereby forming an inhibitor layer; (c) Step C of supplying a second film forming agent to the wafer 200 having the inhibitor layer formed on the surface of the first film to form a second film containing the first element and the second element on the surface of the second base; Do the following.

[0035] Hereinafter, a case will be described in which in step A, a first raw material, a first oxidizing agent, and a first catalyst are supplied to the wafer 200 as the first film-forming agent, and in step C, a second raw material, a second oxidizing agent, and a second catalyst are supplied to the wafer 200 as the second film-forming agent. Specifically, in step A, a cycle including (a1) step A1 of supplying the first raw material and the first catalyst to the wafer 200 and (a2) step A2 of supplying the first oxidizing agent and the first catalyst to the wafer 200 is performed a predetermined number of times (m times, m is an integer of 1 or 2 or more), and in step C, a cycle including (c1) step C1 of supplying the second raw material and the second catalyst to the wafer 200 and (c2) step C2 of supplying the second oxidizing agent and the second catalyst to the wafer 200 is performed a predetermined number of times (n times, n is an integer of 1 or 2 or more).

[0036] In addition, depending on the processing conditions, the supply of the first catalyst may be omitted in at least one of steps A1 and A2, and the supply of the second catalyst may be omitted in at least one of steps C1 and C2. For example, the supply of the first catalyst may be omitted in step A1, the supply of the first catalyst may be omitted in step A2, or the supply of the first catalyst may be omitted in each of steps A1 and A2. For example, in this step, the first raw material and the first oxidizing agent may be used as the first film-forming agent. Also, for example, the supply of the second catalyst may be omitted in step C1, the supply of the second catalyst may be omitted in step C2, or the supply of the second catalyst may be omitted in each of steps C1 and C2. For example, in this step, the second raw material and the second oxidizing agent may be used as the second film-forming agent.

[0037] In the following example, a case will be described in which (d) a step D is further included in which an etching agent is supplied to the wafer 200 after the second film is formed on the surface of the second base, thereby removing the first film. The process performed in step D is also simply called etch-back.

[0038] In this specification, the above-mentioned processing sequence may be expressed as follows for convenience: Similar notations will be used in the following explanations of modified examples and other aspects.

[0039] (First raw material + First catalyst → First oxidant + First catalyst) × m → Modifier → (Second raw material + Second catalyst → Second oxidant + Second catalyst) × n → Etching agent (etch back)

[0040] The term "wafer" used in this specification may mean the wafer itself or a laminate of the wafer and a predetermined layer or film formed on its surface. The term "surface of a wafer" used in this specification may mean the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. When described in this specification, "forming a predetermined layer on a wafer" may mean forming a predetermined layer directly on the surface of the wafer itself or forming a predetermined layer on a layer or the like formed on the wafer. When used in this specification, the term "substrate" is synonymous with the term "wafer".

[0041] As used herein, the term "layer" 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.

[0042] 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, each of the first film-forming agent (first raw material, first oxidizing agent, first catalyst), the second film-forming agent (second raw material, second oxidizing agent, second catalyst), the third film-forming agent (third raw material, third oxidizing agent, third catalyst), the modifier, and the etching agent may include a gaseous substance, a liquid substance such as a mist substance, or both.

[0043] (Wafer charge and boat load) When a plurality of wafers 200 are loaded into the boat 217 (wafer charge), the shutter 219s is moved by the shutter opening / closing mechanism 115s to open the lower end opening of the manifold 209 (shutter open). Thereafter, as shown in FIG. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat load). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b. In this manner, the wafers 200 are prepared in the processing chamber 201.

[0044] (Pressure and temperature regulation) After the boat loading is completed, the inside of the processing chamber 201, i.e., the space in which the wafers 200 are present, is evacuated (reduced pressure exhaust) by the vacuum pump 246 so that the inside of the processing chamber 201 is at a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. Also, the wafers 200 in the processing chamber 201 are heated by the heater 207 so that the wafers 200 are at a desired processing temperature. At this time, the power supply to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. Also, the rotation mechanism 267 starts rotating the wafers 200. The evacuation inside the processing chamber 201 and the heating and rotation of the wafers 200 are all continued at least until the processing of the wafers 200 is completed.

[0045] (Step A) Then, a first film forming agent is supplied to the wafer 200 having a first underlayer and a second underlayer on its surface, thereby forming a first film containing a first element and a second element on the surface of the first underlayer. In this step, specifically, the following steps A1 and A2 are sequentially performed.

[0046] [Step A1] In this step, a first raw material and a first catalyst are supplied to the wafer 200.

[0047] Specifically, the valves 243a and 243b are opened to allow the first raw material and the first catalyst to flow into the gas supply pipes 232a and 232b, respectively. The first raw material and the first catalyst are adjusted in flow rate by the MFCs 241a and 241b, respectively, and are supplied into the processing chamber 201 through the nozzles 249a and 249b, respectively, 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 (supply of the first raw material and the first catalyst). At this time, the valves 243e to 243g may be opened to supply an inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively.

[0048] By supplying the first raw material and the first catalyst to the wafer 200 under processing conditions described below, it becomes possible to selectively (preferentially) chemically adsorb at least a part of the molecular structure of the molecules constituting the first raw material on the surface of the first underlayer out of the surfaces of the first underlayer and the second underlayer. As a result, a first layer is selectively formed on the surface of the first underlayer. The first layer contains at least a part of the molecular structure of the molecules constituting the first raw material, which is a residue derived from the first raw material.

[0049] In this step, the first layer is selectively formed on the surface of the first underlayer by utilizing the property that the incubation time on the surface of the second underlayer is longer than the incubation time on the surface of the first underlayer when the first layer is formed using the first raw material, which is the first film forming agent. The surface of the SiN film, which is the first underlayer, has NH termination or OH termination, and the surface of the Si film, which is the second underlayer, has H termination. When the first layer is formed, the incubation time on the H termination on the surface of the Si film is longer than the incubation time on the NH termination or OH termination on the surface of the SiN film. That is, the first layer is less likely to be formed on the surface of the Si film including H termination than on the surface of the SiN film including NH termination or OH termination. Therefore, in this step, it is possible to selectively (preferentially) form the first layer on the surface of the SiN film, which is the first underlayer, out of the surface of the SiN film, which is the first underlayer, and the surface of the Si film, which is the second underlayer. In addition, for this reason, when attempting to form a first layer on a surface that includes an NH termination, an OH termination, or an H termination, the H termination or the surface that includes an H termination can be said to produce a film formation inhibitory effect (an adsorption inhibitory effect, a reaction inhibitory effect).

[0050] In order to reliably expose the H termination on the surface of the Si film, which is the second underlayer, a process of exposing the surface of the wafer 200 to an etching agent such as an aqueous HF solution (DHF) may be performed in advance. A natural oxide film may be formed on the surface of the Si film, which is the second underlayer. In this case, by performing a process of exposing the surface of the wafer 200 to an etching agent, the natural oxide film on the surface of the Si film can be removed, and the H termination can be reliably exposed on the surface of the Si film. In addition, a natural oxide film may be formed on the surface of the SiN film, which is the first underlayer. In this case, by performing a process of exposing the surface of the wafer 200 to an etching agent, the natural oxide film on the surface of the SiN film can also be removed, and the NH termination and the OH termination can be properly exposed on the surface of the SiN film. In addition, as the etching agent, an etching agent similar to the etching agent used in step D described later can be used, and the etching process at this time can be performed according to the same processing procedure and processing conditions as the etching process in step D described later.

[0051] In this step, the treatment conditions for supplying the first raw material and the first catalyst are as follows: Treatment temperature: room temperature (25°C) to 200°C, preferably 25 to 150°C Treatment pressure: 13 to 2666 Pa, preferably 13 to 1333 Pa Treatment time: 1 to 90 seconds, preferably 1 to 60 seconds First raw material supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm First catalyst supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm Examples are given below.

[0052] In this specification, the expression of a numerical range such as "25 to 200°C" means that the lower limit and the upper limit are included in the range. Therefore, for example, "25 to 200°C" means "25°C or more and 200°C or less". The same applies to other numerical ranges. In this specification, the process temperature means the temperature of the wafer 200 or the temperature in the process chamber 201, and the process pressure means the pressure in the process chamber 201. In addition, the process time means the time that the process continues. In addition, when the supply flow rate includes 0 slm (sccm), 0 slm (sccm) means the case where the gas is not supplied. These are the same in the following description.

[0053] After the first layer is selectively formed on the surface of the first base, the valves 243a and 243b are closed to stop the supply of the first raw material and the first catalyst into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove gaseous substances 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 the processing chamber 201 is purged (purged).

[0054] The processing conditions for purging in this step are as follows: Processing pressure: 1~30Pa Treatment time: 1 to 120 seconds, preferably 1 to 60 seconds Inert gas supply flow rate (per gas supply pipe): 0.5 to 20 slm The treatment temperature during purging is preferably the same as the treatment temperature during supply of the first raw material and the first catalyst.

[0055] As the first raw material, for example, a substance (gas) containing at least one of an amino group, an alkoxy group, and a chloro group can be used. The substance (gas) containing at least one of an amino group, an alkoxy group, and a chloro group is preferably a substance (gas) further containing silicon (Si). The first raw material can be selected according to the type of the first underlayer. For example, when the first underlayer is a film of a single metal element, it is preferable to select a substance (gas) having an amino group and Si.

[0056] The first source material is, for example, tetrakis(dimethylamino)silane (Si[N(CH 3 ) 2 ] 4 ), tris(dimethylamino)silane (Si[N(CH 3 ) 2 ] 3 H), bis(diethylamino)silane (Si[N(C 2 H 5 ) 2 ] 2 H 2 ), bis(tertiary butyl amino) silane (SiH 2 [NH(C 4 H 9 )] 2 ), (diisopropylamino)silane (SiH 3 [N(C 3 H 7 ) 2 ]) and other substances (gases) containing amino groups and Si can be used.

[0057] The first source material is, for example, tetramethoxysilane (Si(OCH 3 ) 4 ), tetraethoxysilane (Si(OC 2 H 5 ) 4 As the first source material, for example, (dimethylamino)trimethoxysilane ((CH 3 ) 2 NSi(OCH 3 ) 3 ), (dimethylamino)triethoxysilane ((CH 3 ) 2 N]Si(OC 2 H 5 ) 3 It is also possible to use a substance (gas) containing an alkoxy group, an amino group, and Si, such as 1,2-dichloro-1,2-triphenylphosphine (1,2-diphenylphosphine), etc. As the first raw material, one or more of these can be used.

[0058] The first raw material may be, for example, bis(trichlorosilyl)methane (SiCl 3 ) 2 CH 2 ), 1,2-bis(trichlorosilyl)ethane ((SiCl 3 ) 2 C 2 H 4 ), 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH 3 ) 2 S 2 Cl 4 ), 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH 3 ) 4 S 2 Cl 2 ), 1,1,3,3-tetrachloro-1,3-disilacyclobutane (C 2 H 4 Cl 4 S 2 The first raw material may be, for example, a substance (gas) containing a chloro group and Si, such as tetrachlorosilane (SiCl 4), hexachlorodisilane (Si 2 Cl 6 ), octachlorotrisilane (Si 3 Cl 8 The first raw material may be, for example, hexachlorodisiloxane (Cl 3 Si-O-SiCl 3 ), Octachlorotrisiloxane (Cl 3 Si-O-SiCl 2 -O-SiCl 3 ) and other substances (gases) containing chloro groups and Si can be used. These substances further contain oxygen. One or more of these can be used as the first raw material.

[0059] 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 (C 5 H 5 N), aminopyridine (C 5 H 6 N 2 ), Picoline (C 6 H 7 N), lutidine (C 7 H 9 N), pyrimidine (C 4 H 4 N 2 ), quinoline (C 9 H 7 N), piperazine (C 4 H 10 N 2 ), piperidine (C 5 H 11 N), pyrrolidine (C 4 H 9 N), aniline (C 6 H 7 A cyclic amine-based substance (cyclic amine-based gas) such as triethylamine (C 2 H 5) 3 N), diethylamine ((C 2 H 5 ) 2 NH), monoethylamine ((C 2 H 5 )NH 2 ), trimethylamine ((CH 3 ) 3 N), dimethylamine ((CH 3 ) 2 NH), monomethylamine ((CH 3 )NH 2 As the first catalyst, one or more of these can be used.

[0060] The inert gas is, for example, nitrogen (N 2 ) gas, or a rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas can be used. As the inert gas, one or more of these can be used. This also applies to each step described later.

[0061] [Step A2] After step A1 is completed, a first oxidant and a first catalyst are supplied to the wafer 200.

[0062] Specifically, the 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 adjusted in flow rate by the MFCs 241c and 241b, respectively, and are supplied into the processing chamber 201 via the nozzles 249c and 249b, respectively, 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 (supply of the first oxidant+first catalyst). At this time, the valves 243e to 243g may be opened to supply an inert gas into the processing chamber 201 via the nozzles 249a to 249c, respectively.

[0063] By supplying the first oxidizing agent and the first catalyst to the wafer 200 under processing conditions described below, it becomes possible to oxidize at least a part of the first layer formed on the surface of the first underlayer in step A1. As a result, a second layer is formed on the surface of the first underlayer by oxidizing the first layer.

[0064] In this step, the treatment conditions for supplying the first oxidant and the first catalyst are as follows: Treatment temperature: room temperature (25°C) to 200°C, preferably 25 to 150°C Treatment pressure: 13 to 2666 Pa, preferably 13 to 1333 Pa Treatment time: 1 to 90 seconds, preferably 1 to 60 seconds First oxidant supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm First catalyst supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm Examples are given below.

[0065] After the first layer formed on the surface of the first base is oxidized and changed (converted) into the second layer, the valves 243c and 243b are closed to stop the supply of the first oxidant and the first catalyst into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 by the same processing procedure and processing conditions as those for purging in step A1. Note that the processing temperature during purging is preferably the same as the processing temperature during supplying the first oxidant and the first catalyst.

[0066] As the first oxidizing agent, for example, a substance containing oxygen (O) and hydrogen (H) (O and H-containing gas) can be used. As the first oxidizing agent, for example, water vapor (H 2 O), hydrogen peroxide (H 2 O 2 ), hydrogen (H 2 ) + oxygen (O 2 ), H 2 +Ozone (O 3In other words, as the O and H containing substance, an O containing substance + H containing substance can be used. In this case, as the H containing substance, H 2 Instead of deuterium (D 2 ) can also be used. As the first oxidizing agent, one or more of these can be used.

[0067] In this specification, "H 2 +O 2 " The description of two substances in parallel is 2 and O 2 When supplying a mixed substance (mixed gas), the two substances may be mixed (premixed) in a supply pipe and then supplied into the processing chamber 201, or the two substances may be separately supplied into the processing chamber 201 through different supply pipes and mixed (postmixed) in the processing chamber 201.

[0068] As the first catalyst, for example, the same catalysts as the various first catalysts exemplified in step A1 above can be used.

[0069] [Perform the specified number of times] A cycle including the above-mentioned step A1 and step A2, specifically, a cycle of performing step A1 and step A2 non-simultaneously (alternately) is performed a predetermined number of times (m times, m is an integer of 1 or 2 or more). As a result, as shown in FIG. 4(b), a first film including a first element and a second element can be selectively formed on the surface of the first underlayer among the surface of the first underlayer and the surface of the second underlayer of the wafer 200. For example, when the above-mentioned first raw material, first oxidizing agent, and first catalyst are used, a silicon oxide film (SiO film), a silicon oxycarbide film (SiOC film), or a silicon oxycarbonitride film (SiOCN film), which is an oxide film, can be selectively grown on the surface of the first underlayer. In this way, for example, a first film including a first element being silicon (Si) and a second element being oxygen (O) can be selectively grown on the surface of the first underlayer. The first film may further include carbon (C) or nitrogen (N).

[0070] In addition, it is preferable to repeat the above-mentioned cycle multiple times, that is, it is preferable to make the thickness of the second layer formed in each cycle thinner than the desired thickness of the first film, and to repeat the above-mentioned cycle multiple times until the thickness of the first film formed by laminating the second layer reaches the desired thickness.

[0071] In addition, when performing steps A1 and A2, the formation and growth of the first film on the surface of the second underlayer may occur very slightly. However, even in this case, the thickness of the first film formed on the surface of the second underlayer is much thinner than the thickness of the first film formed on the surface of the first underlayer. In this specification, "selectively (preferentially) forming a first film on the surface of the first underlayer" includes not only a case where no first film is formed on the surface of the second underlayer and the first film is formed only on the surface of the first underlayer, but also a case where a very thin first film is formed on the surface of the second underlayer, but a much thicker first film is formed on the surface of the first underlayer.

[0072] In this step, it is desirable to set the thickness of the first film formed on the surface of the first underlayer to 0.5 nm or more and 10 nm or less, preferably 1 nm or more and 5 nm or less, and more preferably 1.5 nm or more and 3 nm or less.

[0073] If the thickness of the first film is less than 0.5 nm, the amount of at least a part of the molecular structure of the molecules constituting the modifier adsorbed on the surface of the first film (residues derived from the modifier) ​​may be insufficient in step B described below. In this case, the adsorption suppression effect of the inhibitor layer formed on the surface of the first film may be insufficient. This problem can be solved by making the thickness of the first film 0.5 nm or more. This problem can be solved effectively by making the thickness of the first film 1 nm or more. This problem can be solved more effectively by making the thickness of the first film 1.5 nm or more.

[0074] If the thickness of the first film is made thicker than 10 nm, the action of the first film-forming agent may disable the adsorption suppression effect of at least a part of the H-terminus on the surface of the second underlayer, and the adsorption suppression effect of the H-terminus may become insufficient. As a result, the first film may be formed on the surface of the second underlayer as well, and in the subsequent step B, an inhibitor layer may be formed on the surface of the second underlayer as well. By making the thickness of the first film 10 nm or less, it is possible to solve this problem. By making the thickness of the first film 5 nm or less, it is possible to effectively solve this problem. By making the thickness of the first film 3 nm or less, it is possible to more effectively solve this problem.

[0075] 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. In this step, the thickness of the first film is preferably equal to or less than the thickness of the second film formed in step C described later, and more preferably thinner than the thickness of the second film formed in step C. That is, in this step, the thickness of the first film is preferably different from the thickness of the second film formed in step B, and more preferably thinner than the thickness of the second film. This increases the film thickness difference between the first film formed on the surface of the first underlayer and the second film formed on the surface of the second underlayer (i.e., the thickness of the second film - the thickness of the first film), making it possible to increase the selectivity. In addition, the ratio of the thickness of the second film formed on the surface of the second underlayer to the thickness of the first film formed on the surface of the first underlayer also increases, making it possible to increase the selectivity.

[0076] Furthermore, if the first film is made too thick, in this step, detachment of H-terminus on the surface of the second underlayer or replacement of H-terminus with another terminus occurs, and an inhibitor layer is formed not only on the surface of the first film but also on the surface of the second underlayer in step B, which may inhibit the growth of the second film on the surface of the second underlayer in step C. For this reason, it is preferable that the thickness of the first film formed in this step is thinner than the thickness of the second film formed in step C.

[0077] In addition, in this step, it is preferable to set the film formation conditions of the first film to conditions under which the reaction occurs slowly, i.e., conditions under which the reactivity and the degree of reaction are low, so that the H-terminus is left on the surface of the second underlayer. In this step, if the film formation conditions of the first film are conditions under which the reactivity and the degree of reaction are high, the H-terminus on the surface of the second underlayer may be detached or replaced with another terminus, and in step B, an inhibitor layer may be formed not only on the surface of the first film but also on the surface of the second underlayer, which may inhibit the growth of the second film on the surface of the second underlayer in step C. For this reason, in this step, it is preferable to set the film formation conditions of the first film to conditions under which the reaction occurs slowly.

[0078] Specifically, for example, by performing this step under at least one of the following processing conditions, the film formation conditions in this step can be set to conditions under which the reaction occurs slowly, and it becomes possible to leave H termination on the surface of the second underlayer. In addition, by using at least one of the following processing conditions, this step is performed under processing conditions that result in a lower film formation rate than step C described below. The processing temperature in step A (step A1, step A2) is set higher than the processing temperature in step C (step C1, step C2). The processing pressure in step A (step A1, step A2) is set lower than the processing pressure in step C (step C1, step C2). The first raw material supply flow rate in step A1 is set to be smaller than the second raw material supply flow rate in step C1. The first oxidant supply flow rate in step A2 is set to be smaller than the second oxidant supply flow rate in step C2. The time period during which the first raw material is supplied in step A1 is set shorter than the time period during which the second raw material is supplied in step C1. The supply time of the first oxidant in step A2 is set shorter than the supply time of the second oxidant in step C2.

[0079] (Step B) Thereafter, a modifying agent is supplied to the wafer 200, so that at least a part of the molecular structure of molecules constituting the modifying agent is adsorbed onto the surface of the first film formed on the surface of the first underlayer, thereby forming an inhibitor layer.

[0080] Specifically, the valve 243d is opened to allow the modifying agent to flow into the gas supply pipe 232d. The modifying agent is adjusted in flow rate by the MFC 241d, supplied into the processing chamber 201 via the nozzle 249a, and exhausted from the exhaust port 231a. At this time, the modifying agent is supplied to the wafer 200 from the side of the wafer 200 (modifying agent supply). At this time, the valves 243e to 243g may be opened to supply an inert gas into the processing chamber 201 via each of the nozzles 249a to 249c.

[0081] By supplying the modifying agent to the wafer 200 under processing conditions described below, it is possible to selectively (preferentially) adsorb at least a part of the molecular structure of the molecules constituting the modifying agent to the surface of the first film out of the surface of the first film and the surface of the second underlayer. As a result, as shown in FIG. 4(c), an inhibitor layer is selectively formed on the surface of the first film formed on the surface of the first underlayer. That is, in this step, 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 selectively adsorbed to the surface of the first film, and the surface of the first film can be modified to form an inhibitor layer.

[0082] In this step, the inhibitor layer is selectively formed on the surface of the first film by utilizing the property that the incubation time on the surface of the second underlayer is longer than the incubation time on the surface of the first film when the inhibitor layer is formed using a modifier. As described above, in step A, an oxide film such as a SiO film, a SiOC film, or a SiOCN film is formed as the first film on the surface of the first underlayer. The surface of this oxide film includes OH terminations, and the surface of the Si film, which is the second underlayer, includes H terminations. When the inhibitor layer is formed, the incubation time on the H terminations on the surface of the Si film is longer than the incubation time on the OH terminations on the surface of the oxide film. That is, the inhibitor layer is less likely to be formed on the surface of the Si film including H terminations than on the surface of the oxide film including OH terminations. Therefore, in this step, it is possible to selectively (preferentially) form the inhibitor layer on the surface of the oxide film, which is the first film, out of the surface of the oxide film, which is the first film, and the surface of the Si film, which is the second underlayer. In addition, for these reasons, when attempting to form an inhibitor layer on a surface that contains OH or H terminations, the H terminations or surfaces that contain H terminations can be said to produce a film formation inhibitory effect (adsorption inhibitory effect, reaction inhibitory effect).

[0083] The inhibitor layer formed in this step contains at least a part of the molecular structure of the molecule constituting the modifier, which is a residue derived from the modifier. The inhibitor layer prevents the second film-forming agent (second raw material) from adsorbing to the surface of the first film in step C described below, and inhibits (suppresses) the progress of the film-forming reaction on the surface of the first film. For this reason, the inhibitor layer is also called a film-formation inhibition layer (adsorption inhibition layer, reaction inhibition layer).

[0084] At least a part of the molecular structure of the molecule constituting the modifier is, for example, a trimethylsilyl group (-SiMe 3 ) and triethylsilyl group (-SiEt 3) can be exemplified. In these cases, the surface of the first film is terminated with an alkyl group such as a methyl group or an ethyl group. The alkyl group (alkylsilyl group) such as a methyl group (trimethylsilyl group) or an ethyl group (triethylsilyl group) that terminates the surface of the first film constitutes an inhibitor layer, which prevents the second film-forming agent (second raw material) from being adsorbed onto the surface of the first film in step C described below, and can inhibit (suppress) the progress of the film-forming reaction on the surface of the first film.

[0085] In addition, the term "inhibitor" as used in this specification may mean a film formation inhibitory effect (adsorption inhibitory effect, reaction inhibitory effect), as well as a modifier or a residue derived from a modifier, for example, at least a part of the molecular structure of a molecule that constitutes a modifier, and may also be used as a collective term for all of these.

[0086] The processing conditions for supplying the modifier in this step are as follows: Treatment temperature: room temperature (25°C) to 500°C, preferably 25 to 250°C Treatment pressure: 5 to 2000 Pa, preferably 10 to 1000 Pa Processing time: 1 second to 120 minutes, preferably 30 seconds to 60 minutes Modifier supply flow rate: 0.001 to 3 slm, preferably 0.001 to 0.5 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm Examples are given below.

[0087] After the inhibitor layer is formed on the surface of the first film, the valve 243d is closed to stop the supply of the modifying agent into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 (purging) by the same processing procedure and processing conditions as those for purging in step A1. Note that the processing temperature during purging is preferably the same as the processing temperature during supply of the modifying agent.

[0088] The modifier may be, for example, (dimethylamino)trimethylsilane ((CH 3 )2 NSi(CH 3 ) 3 ), (diethylamino)triethylsilane ((C 2 H 5 ) 2 NSi(C 2 H 5 ) 3 ), (dimethylamino)triethylsilane ((CH 3 ) 2 NSi(C 2 H 5 ) 3 ), (diethylamino)trimethylsilane ((C 2 H 5 ) 2 NSi(CH 3 ) 3 ), (dipropylamino)trimethylsilane ((C 3 H 7 ) 2 NSi(CH 3 ) 3 ), (dibutylamino)trimethylsilane ((C 4 H 9 ) 2 NSi(CH 3 ) 3 ), (trimethylsilyl)amine ((CH 3 ) 3 SiNH 2 ), (triethylsilyl)amine ((C 2 H 5 ) 3 SiNH 2 ), (dimethylamino)silane ((CH 3 ) 2 NSiH 3 ), (diethylamino)silane ((C 2 H 5 ) 2 NSiH 3 ), (dipropylamino)silane ((C 3 H 7 ) 2 NSiH 3 ), (dibutylamino)silane ((C 4 H 9 ) 2 NSiH 3) etc. As the modifier, one or more of these can be used.

[0089] In addition, examples of the modifier include bis(dimethylamino)dimethylsilane ([(CH 3 ) 2 N] 2 Si(CH 3 ) 2 ), bis(diethylamino)diethylsilane ([(C 2 H 5 ) 2 N] 2 Si(C 2 H 5 ) 2 ), bis(dimethylamino)diethylsilane ([(CH 3 ) 2 N] 2 Si(C 2 H 5 ) 2 ), bis(diethylamino)dimethylsilane ([(C 2 H 5 ) 2 N] 2 Si(CH 3 ) 2 ), bis(dimethylamino)silane ([(CH 3 ) 2 N] 2 SiH 2 ), bis(diethylamino)silane ([(C 2 H 5 ) 2 N] 2 SiH 2 ), bis(dimethylaminodimethylsilyl)ethane ([(CH 3 ) 2 N(CH 3 ) 2 Si] 2 C 2 H 6 ), bis(dipropylamino)silane ([(C 3 H 7 ) 2 N] 2 SiH 2 ), bis(dibutylamino)silane ([(C 4 H 9 ) 2 N]2 SiH 2 ), bis(dipropylamino)dimethylsilane ([(C 3 H 7 ) 2 N] 2 Si(CH 3 ) 2 ), bis(dipropylamino)diethylsilane ([(C 3 H 7 ) 2 N] 2 Si(C 2 H 5 ) 2 ), (dimethylsilyl)diamine ((CH 3 ) 2 Si(NH 2 ) 2 ), (diethylsilyl)diamine ((C 2 H 5 ) 2 Si(NH 2 ) 2 ), (dipropylsilyl)diamine ((C 3 H 7 ) 2 Si(NH 2 ) 2 ), bis(dimethylaminodimethylsilyl)methane ([(CH 3 ) 2 N(CH 3 ) 2 Si] 2 CH 2 ), bis(dimethylamino)tetramethyldisilane ([(CH 3 ) 2 N] 2 (CH 3 ) 4 S 2 ) etc. As the modifier, one or more of these can be used.

[0090] In addition, when carrying out this step, at least a part of the molecular structure of the molecules constituting the modifier may be adsorbed on a part of the surface of the second undercoat. However, even in this case, the amount of adsorption is small, and the amount of adsorption on the surface of the first film is overwhelmingly larger. 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" includes not only the case where at least a part of the molecular structure of the molecules constituting the modifier is not adsorbed at all on the surface of the second undercoat, but at least a part of the molecular structure of the molecules constituting the modifier is adsorbed only on the surface of the first film, but also the case where at least a very small amount of at least a part of the molecular structure of the molecules constituting the modifier is adsorbed on the surface of the second undercoat, but at least a much larger amount of at least a part of the molecular structure of the molecules constituting the modifier is adsorbed on the surface of the first film.

[0091] (Step C) Then, a second film-forming agent is supplied to the wafer 200 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, as shown in Fig. 4(d). In this step, specifically, the following steps C1 and C2 are sequentially performed.

[0092] [Step C1] In this step, the second raw material and the second catalyst are supplied to the wafer 200. The processing procedure at this time can be the same as the processing procedure in step A1.

[0093] By supplying the second source material and the second catalyst to the wafer 200 under processing conditions described below, it becomes possible to selectively (preferentially) chemically adsorb at least a part of the molecular structure of the molecules constituting the second source material onto the surface of the second base material out of the surface of the inhibitor layer and the surface of the second base material. As a result, a third layer is selectively formed on the surface of the second base material. The third layer contains at least a part of the molecular structure of the molecules constituting the second source material, which is a residue derived from the second source material.

[0094] In this step, the third layer is selectively formed on the surface of the second underlayer by utilizing 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 underlayer when the third layer is formed using the second raw material, which is the second film forming agent. The surface of the Si film, which is the second underlayer, contains H termination as described above, and the surface of the inhibitor layer contains alkyl termination as described above. When the third layer is formed, the incubation time on the alkyl termination on the surface of the inhibitor layer is longer than the incubation time on the H termination on the surface of the Si film. That is, the third layer is less likely to be formed on the surface of the inhibitor layer containing alkyl termination than on the surface of the Si film containing H termination. Therefore, in this step, it is possible to selectively (preferentially) form the third layer on the surface of the Si film, which is the second underlayer, out of the surface of the Si film, which is the second underlayer, and the surface of the inhibitor layer. In addition, for these reasons, when attempting to form a third layer on a surface that includes an H termination or an alkyl group termination, the alkyl group termination or the surface that includes an alkyl group termination can be said to produce a film formation inhibitory effect (adsorption inhibitory effect, reaction inhibitory effect).

[0095] In this step, the treatment conditions for supplying the second raw material and the second catalyst are as follows: Treatment temperature: room temperature (25°C) to 200°C, preferably 25 to 150°C Treatment pressure: 133 to 4000 Pa, preferably 133 to 2666 Pa Treatment time: 1 to 120 seconds, preferably 1 to 90 seconds Second raw material supply flow rate: 0.001 to 3 slm, preferably 0.01 to 2 slm Second catalyst supply flow rate: 0.001 to 3 slm, preferably 0.01 to 2 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm Examples are given below.

[0096] After the third layer is formed on the surface of the second base, the supply of the second raw material and the second catalyst into the processing chamber 201 is stopped. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 (purging) by the same processing procedure and processing conditions as those for purging in step A1. Note that the processing temperature during purging is preferably the same as the processing temperature during supplying the second raw material and the second catalyst.

[0097] The second raw material may be, for example, the same raw material as the various first raw materials exemplified in step A1 above. 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.

[0098] The second catalyst may be, for example, the same catalyst as the various first catalysts exemplified in step A1 above. The second catalyst may be the same substance as the first catalyst used in step A1 or may be a different substance, but is preferably the same substance.

[0099] [Step C2] After step C1 is completed, a second oxidant and a second catalyst are supplied to the wafer 200. The processing procedure at this time can be the same as the processing procedure in step A2.

[0100] By supplying the second oxidizing agent and the second catalyst to the wafer 200 under processing conditions described below, it becomes possible to oxidize at least a part of the third layer formed on the surface of the second underlayer in step C1. As a result, a fourth layer is formed on the surface of the second underlayer by oxidizing the third layer.

[0101] The treatment conditions for supplying the second oxidant and the second catalyst in this step are as follows: Treatment temperature: room temperature (25°C) to 200°C, preferably 25 to 150°C Treatment pressure: 133 to 4000 Pa, preferably 133 to 2666 Pa Treatment time: 1 to 120 seconds, preferably 1 to 90 seconds Second oxidant supply flow rate: 0.001 to 3 slm, preferably 0.01 to 2 slm Second catalyst supply flow rate: 0.001 to 3 slm, preferably 0.01 to 2 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm Examples are given below.

[0102] After the fourth layer is formed on the surface of the second base, the supply of the second oxidant and the second catalyst into the processing chamber 201 is stopped. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 (purging) by the same processing procedure and processing conditions as those for purging in step A1. Note that the processing temperature during purging is preferably the same as the processing temperature during supplying the second oxidant and the second catalyst.

[0103] The second oxidizing agent may be, for example, the same oxidizing agent as the various first oxidizing agents exemplified in step A2 above. The second oxidizing agent may be the same substance as the first oxidizing agent used in step A2 or may be a different substance, but is preferably the same substance.

[0104] The second catalyst may be, for example, the same catalyst as the various first catalysts exemplified in step A1 above. The second catalyst may be the same material as the first catalyst used in step A1 or may be a different material, but is preferably the same material.

[0105] [Perform the specified number of times] A cycle including the above-mentioned step C1 and step C2, specifically, a cycle of performing step C1 and step C2 non-simultaneously (alternately) is performed a predetermined number of times (n times, n is an integer of 1 or 2 or more). As a result, as shown in FIG. 4(d), a second film including a first element and a second element can be selectively formed on the surface of the second underlayer out of the surface of the first underlayer and the surface of the second underlayer of the wafer 200. For example, when the above-mentioned second raw material, second oxidizing agent, and second catalyst are used, an oxide film, such as a SiO film, a SiOC film, or a SiOCN film, can be selectively grown on the surface of the second underlayer. In this way, a second film, for example, in which the first element is Si and the second element is O, can be selectively grown on the surface of the second underlayer. The first film may further include C or N.

[0106] Both the first film and the second film contain the first element and the second element. The second film may be made of the same material as the first film. For example, in the above example, both the first film and the second film may be SiO films, or both may be SiOC films, or both may be SiOCN films. The second film may have the same composition ratio (ratio of constituent elements) as the first film. The second film may be made of a different material than the first film. For example, in the above example, the first film may be a SiO film and the second film may be a SiOC film, or the first film may be a SiO film and the second film may be a SiOCN film.

[0107] In addition, it is preferable to repeat the above-mentioned cycle multiple times, that is, it is preferable to make the thickness of the fourth layer formed in each cycle thinner than the desired thickness of the second film, and to repeat the above-mentioned cycle multiple times until the thickness of the second film formed by laminating the fourth layer reaches the desired thickness.

[0108] In addition, when performing steps C1 and C2, the formation and growth of the second film on the surface of the inhibitor layer may occur very slightly. 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 underlayer. In this specification, "selectively (preferentially) forming a second film on the surface of the second underlayer" includes not only the case where no second film is formed on the surface of the inhibitor layer and the second film is formed only on the surface of the second underlayer, but also the case where a very thin second film is formed on the surface of the inhibitor layer, but a much thicker second film is formed on the surface of the second underlayer.

[0109] In this step, it is desirable to increase the thickness of the second film formed on the surface of the second underlayer to improve selectivity. The thickness of the second film is desirably, for example, 0.5 nm to 15 nm. Note that the second film formed in this step may be etched in the same manner as the first film in step D described below. Therefore, it is desirable to increase the thickness of the second film in this step, taking into account the amount to be etched in step D.

[0110] (Step D) Thereafter, an etching agent is supplied to the wafer 200 after the second film is formed on the surface of the second base, thereby removing the first film.

[0111] Specifically, the valve 243h is opened to allow the etching agent to flow into the gas supply pipe 232h. The flow rate of the etching agent is adjusted by the MFC 241h, and the etching agent is supplied into the processing chamber 201 through the nozzle 249a and exhausted from the exhaust port 231a. At this time, the etching agent is supplied to the wafer 200 from the side of the wafer 200 (etching agent supply). At this time, the valves 243e to 243g may be opened to supply an inert gas into the processing chamber 201 through each of the nozzles 249a to 249c.

[0112] By supplying an etching agent to the wafer 200 under processing conditions described below, the first film formed on the surface of the first underlayer can be removed (etched) to expose the surface of the first underlayer. When the first film is removed, the inhibitor layer remaining on the surface of the first film is also removed. As a result, the surface of the first underlayer of the wafer 200 is exposed as shown in FIG. 4(e).

[0113] The processing conditions for supplying the etching agent in this step are as follows: Treatment temperature: room temperature (25°C) to 400°C, preferably 50 to 200°C Treatment pressure: 1 to 13332 Pa, preferably 100 to 1333 Pa Treatment time: 0.1 to 60 minutes, preferably 1 to 30 minutes Etching agent supply flow rate: 0.05 to 5 slm, preferably 0.1 to 2 slm Inert gas supply flow rate (per gas supply pipe): 1 to 10 slm, preferably 2 to 10 slm Examples are given below.

[0114] After removing the first film on the surface of the first undercoat, the valve 243h is closed to stop the supply of the etching agent into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 (purging) by the same processing procedure and processing conditions as those for purging in step A1. Note that the processing temperature during purging is preferably the same as the processing temperature during supply of the etching agent.

[0115] As the etching agent, for example, a fluorine (F)-containing substance (F-containing gas) can be used. As the etching agent, for example, chlorine trifluoride (ClF 3 ), chlorine fluoride (ClF), nitrogen fluoride (NF 3 ), fluorine (F 2 For example, F-containing substances (F-containing gases) such as hydrogen fluoride (HF), dihydrogen fluoride (DHF), etc. As the etching agent, one or more of these can be used.

[0116] (After purging and atmospheric pressure recovery) After step D is completed, an inert gas is supplied as a purge gas from each of the nozzles 249a to 249c into the processing chamber 201 and exhausted from the exhaust port 231a. This purges the processing chamber 201, and gases and reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (after-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

[0117] (Boat unloading and wafer discharging) Thereafter, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafers 200 are carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the boat 217 (boat unloading). After the boat unloading, the shutter 219s is moved, and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). After being carried out to the outside of the reaction tube 203, the processed wafers 200 are taken out of the boat 217 (wafer discharge).

[0118] (3) Effects of this mode According to this aspect, one or more of the following effects can be obtained.

[0119] By carrying out steps A, B, and C, the second film can be selectively formed on the surface of the second underlayer with high accuracy. This is because the incubation time on the surface of the second underlayer is longer than the incubation time on each surface of the first underlayer 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 underlayer. That is, the incubation time on the surface of the inhibitor layer is the longest, the incubation time on the surface of the second underlayer is the next longest, and the incubation time on each surface of the first underlayer and the first film is the shortest. In this way, by controlling the balance of the incubation times on each surface, the first film can be selectively formed on the surface of the first underlayer in step A, the inhibitor layer can be selectively formed on the surface of the first film in step B, and the second film can be selectively formed on the surface of the second underlayer with high accuracy in step C. That is, according to this aspect, it is possible to selectively form a desired film on a desired surface with high precision.

[0120] By carrying out steps A, B, and C, a first film containing a first element and a second element is formed on the surface of a first base, an inhibitor layer is formed on the surface of the first film, and a second film containing a first element and a second element is formed on the surface of a second base. For example, when the first film contains a first element and a second element and the second film contains a third element and a fourth element, the third element or the fourth element may be mixed into the first film, or the first element or the second element may be mixed into the second film, that is, cross-contamination may occur, and the film characteristics may be deteriorated. In contrast, when the first film and the second film each contain the same element, that is, the first element and the second element, the above-mentioned cross-contamination can be prevented and the film characteristics can be improved. This effect is particularly noticeable when the first film and the second film are formed in the same processing chamber (in-situ).

[0121] In addition, since the first film and the second film each contain the first element and the second element, when the first film is etched back with an etching agent after the formation of the second film, that is, when step D is performed after step C, the thickness of the second film that is exposed to the etching agent together with the first film can be controlled with high controllability. In addition, since the first film and the second film each contain the first element and the second element, the supply system of the first film forming agent for forming the first film and the supply system of the second film forming agent for forming the second film can be shared, and the supply system can be simplified. This makes it possible to significantly reduce the cost of the device and simplify the maintenance of the device. In addition, since the first film and the second film each contain the first element and the second element, the film forming temperature of the first film and the film forming temperature of the second film can be made equal, and when the processing of steps A, B, and C is repeated for different wafers 200, that is, when different wafers 200 are continuously processed, the throughput can be improved, and the productivity in the continuous processing can be improved.

[0122] It is preferable that the first film is an oxide film and the second film is an oxide film, more preferably that the first element is Si and the second element is O, and it is particularly preferable 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. This makes it possible to effectively produce the above-mentioned effects. It is also possible to make the first film and the second film have the same material (molecular structure, constituent elements) as when both the first film and the second film are 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 that the thickness of the second film can be controlled with higher controllability. It is also possible to make the materials of the two different from each other as when the first film is a SiO film and the second film is a SiOC film or a SiOCN film. In this case, by using a SiO film as the first film and a SiOC film or a SiOCN film as the second film, when performing step D after performing step C, the etching of the second film can be suppressed due to the effect that the second film contains C or N, and it becomes possible to selectively etch the first film. This allows for even higher controllability in the thickness of the second film, which is exposed to the etching agent together with the first film when etching the first film.

[0123] In step A, it is preferable to supply the first raw material and the first oxidizing agent to the wafer 200 as the first film forming agent, and in step C, it is preferable to supply the second raw material and the second oxidizing agent to the wafer 200 as the second film forming agent. Specifically, in step A, it is preferable to perform a cycle including step A1 of supplying the first raw material to the wafer 200 and step A2 of supplying the first oxidizing agent to the wafer 200 a predetermined number of times, and in step C, it is preferable to perform a cycle including step C1 of supplying the second raw material to the wafer 200 and step C2 of supplying the second oxidizing agent to the wafer 200 a predetermined number of times. In at least one of steps A1 and A2, it is preferable to further supply the first catalyst, and in at least one of steps C1 and C2, it is preferable to further supply the second catalyst. This makes it possible to effectively produce the above-mentioned effects. In addition, the action of each catalyst makes it possible to lower the processing temperature in each step, and to soften the reaction occurring in each step, and to improve the selectivity in the selective growth of the first film and the second film.

[0124] The first raw material and the second raw material are preferably substances containing at least one of an amino group, an alkoxy group, and a chloro group, and the first oxidizing agent and the second oxidizing agent are preferably substances containing O and H. The first raw material and the second raw material may be the same substance or different substances. The first oxidizing agent and the second oxidizing agent may be the same substance or different substances. It is more preferable that the first raw material and the second raw material are the same substance, and the first oxidizing agent and the second oxidizing agent are the same substance. In addition, when the first catalyst and the second catalyst are used, it is more preferable that the first raw material and the second raw material are the same substance, the first oxidizing agent and the second oxidizing agent are the same substance, and the first catalyst and the second catalyst are the same substance. These can also be said to be cases in which the first film-forming agent and the second film-forming agent are the same substance. This makes it possible to effectively produce the above-mentioned effects.

[0125] It is preferable to set the thickness of the first film to be equal to or less than the thickness of the second film, or to set the thickness of the first film to be thinner than the thickness of the second film. It is also preferable to perform step A under processing conditions that result in a lower film formation rate than step C. This makes it possible to make the reaction when forming the first film gentler than the reaction when forming the second film, and to increase the ratio of the thickness of the second film formed on the surface of the second underlayer to the thickness of the first film formed on the surface of the first underlayer, thereby making it possible to increase the selectivity.

[0126] It is preferable to set the temperature of the wafer 200 to the same in steps A, B, and C. That is, it is preferable to set the processing temperature to the same in steps A, B, and C. This makes it possible to effectively achieve the above-mentioned effect on productivity.

[0127] Also, it is preferable to perform step A, step B, and step C in the same space. That is, as described above, it is preferable to perform step A, step B, and step C in the same processing chamber (in-situ). This allows step A, step B, and step C to be performed continuously without a process of transporting the wafer 200 between them. This allows the throughput to be improved, and the productivity to 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 steps, and it is possible to prevent defects such as deterioration of selectivity due to exposure to the atmosphere, and it is possible to perform selective growth appropriately. Note that, as described above, in addition to step A, step B, and step C, it is also preferable to perform step D in the same space (in the same processing chamber).

[0128] (4) Variations The processing sequence in this embodiment can be modified as shown in the following modified examples. These modified examples can be combined as desired. Unless otherwise specified, the processing procedure and processing conditions in each step of each modified example can be the same as the processing procedure and processing conditions in each step of the above-mentioned processing sequence.

[0129] (Variation 1) As in the processing sequence shown below, in cases where it is not necessary to remove the first film formed on the surface of the first underlayer, step D can be omitted. In this modified example, the same effects as those of the above-mentioned embodiment can be obtained.

[0130] (First raw material + First catalyst → First oxidant + First catalyst) × m → Reformer → (Second raw material + Second catalyst → Second oxidant + Second catalyst) × n

[0131] (Variation 2) (e) Step E may be further performed to form a third film on the second film 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 will be described in which a third raw material, a third oxidizing agent, and a third catalyst are supplied to the wafer 200 as the third film-forming agent in step E. In this case, it is preferable that a cycle including (e1) step E1 of supplying the third raw material and the third catalyst to the wafer 200 and (e2) step E2 of supplying the third oxidizing agent and the third catalyst to the wafer 200 is performed a predetermined number of times (p times, p is an integer of 1 or 2 or more) in step E1 and step E2, as shown in the processing sequence below. Note that the supply of the third catalyst may be omitted in at least one of steps E1 and E2.

[0132] (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 → Etching agent (etch back)

[0133] This modified example will be described mainly with reference to FIG. 5(a) to FIG. 5(f). First, a wafer 200 having a first underlayer and a second underlayer on its surface as shown in FIG. 5(a) is used, as in the above embodiment. Step A is performed using this wafer 200, and a first film is selectively formed on the surface of the first underlayer as shown in FIG. 5(b). Then, step B is performed, and an inhibitor layer is formed on the surface of the first film as shown in FIG. 5(c). Then, step C is performed, and a second film is selectively formed on the surface of the second underlayer as shown in FIG. 5(d). Then, step E is performed, and a third film is selectively formed on the surface of the second film as shown in FIG. 5(e). Then, step D is performed, and the first film formed on the surface of the first underlayer is removed together with the inhibitor layer as shown in FIG. 5(f). In this way, a laminated film is formed by selectively laminating the second film and the third film on the surface of the second underlayer out of the surfaces of the first underlayer and the second underlayer of the wafer 200.

[0134] The processing procedure and processing conditions of step E in this modification can be the same as those of step C in the above processing sequence, except that a third film-forming agent (third raw material, third oxidizing agent, third catalyst) is used and the target to which the third film-forming agent is supplied is the wafer 200 after step C. The third raw material can be, for example, the same raw material as the various first raw materials exemplified in step A1 above. The third oxidizing agent can be, for example, the same oxidizing agent as the various first oxidizing agents exemplified in step A2 above. The third catalyst can be, for example, the same catalyst as the various first catalysts exemplified in step A1 above. Note that the third film-forming agent (third raw material, third oxidizing agent, third catalyst) is preferably a different substance from the second film-forming agent (second raw material, second oxidizing agent, second catalyst). Also, it is preferable that the third film is made of a different material from the second film. Also, it is preferable that the third film is made of a different material from the first film. For example, when the first film is a SiO film and the second film is a SiO film, the third film can be a SiOC film or a SiOCN film. Also, 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.

[0135] In this modification, the same effect as that of the above-mentioned embodiment can be obtained. In addition, in this modification, by forming a third film on the second film, when the first film is etched back by an etching agent after the formation of the second film, the third film can act as an etching block film (cap film, etching barrier film, etching inhibitor film). For this reason, it is preferable that the third film has a higher etching resistance than the second film. It is also preferable that the third film has a higher etching resistance than the first film. For example, by making the third film a film containing C or N such as a SiOC film or a SiOCN film, the third film can be made a film with high etching resistance. This allows the first film to be selectively etched without etching the second film, and even when the first film is etched back, the thickness of the second film can be controlled with high controllability.

[0136] <Other Aspects of the Disclosure> Although the embodiments of the present disclosure have been specifically described above, the present disclosure is not limited to the above embodiments and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0137] For example, the wafer 200 may have a plurality of regions of different materials as the first underlayer, and may have a plurality of regions of different materials as the second underlayer. In the wafer 200, any underlayer can be used as the first underlayer as long as it includes a surface (end) having a shorter incubation time when forming the first film compared to the second underlayer. That is, in the wafer 200, any underlayer can be used as the first underlayer and the second underlayer as long as it includes at least two types of surfaces having different incubation times when forming the first film. For example, it is preferable that the first underlayer includes an insulating film, and the second underlayer includes at least one of a semiconductor substrate, a semiconductor element single film, and a metal element single film. In addition, it is preferable that the insulating film includes at least one of a semiconductor insulating film and a metal insulating film. In these cases, when forming the first film, it is possible to appropriately generate the above-mentioned difference in incubation time on each surface of the first underlayer and the second underlayer. In this embodiment, the same effect as the above-mentioned embodiment can be obtained.

[0138] The first underlayer may be a semiconductor insulating film such as the above-mentioned SiN film, SiO film (including a natural oxide film), SiOC film, SiOCN film, silicon oxynitride film (SiON film), silicon carbide film (SiC film), silicon carbonitride film (SiCN film), silicon boronitride film (SiBN film), silicon boron carbonitride film (SiBCN film), other Si-based insulating films, or a metal insulating film such as a hafnium oxide film (HfO film), zirconium oxide film (ZrO film), aluminum oxide film (AlO film), or other metal-based oxide film. At least one of these can be used as the first underlayer.

[0139] The second underlayer may be a semiconductor substrate such as a Si wafer (single crystal Si) in addition to the above-mentioned Si film. The Si film includes a semiconductor element single film such as an amorphous silicon film (a-Si film), a polysilicon film (poly-Si film), a mixed crystal film of amorphous silicon and polysilicon, and an epitaxial silicon film (Epi-Si film). The second underlayer may 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), or a molybdenum film (Mo film). At least one of these can be used as the second underlayer.

[0140] In the above-mentioned embodiment, the above-mentioned processing sequence is performed in the same processing chamber of the same processing apparatus (in-situ). The present disclosure is not limited to the above-mentioned embodiment, and for example, one step of the above-mentioned processing sequence and another step may be performed in different processing chambers of different processing apparatuses (ex-situ), or may be performed in different processing chambers of the same processing apparatus. In these cases, the same effects as those in the above-mentioned embodiment can be obtained.

[0141] In the various cases described above, if a series of steps are performed in-situ, the wafer 200 is not exposed to the atmosphere during the process, and the wafer 200 can be consistently processed while being placed under vacuum, allowing for stable processing. Also, if some steps are performed ex-situ, the temperature in each processing chamber can be preset to, for example, the processing temperature in each step or a temperature close to the processing temperature, thereby shortening the time required for temperature adjustment and improving throughput, i.e., productivity.

[0142] It is preferable that the recipes used for each process are prepared individually according to the process contents, and are recorded and stored in the storage device 121c via an electric communication line or an external storage device 123. Then, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the process contents from among the multiple recipes recorded and stored in the storage device 121c. This makes it possible to form films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility in the processing device. It is also possible to reduce the burden on the operator, and to quickly start each process while avoiding operational errors.

[0143] The above-mentioned recipes are not limited to being newly created, but may be prepared, for example, by modifying an existing recipe that has already been installed in the processing device. When modifying a recipe, the modified recipe may be installed in the processing device via an electric communication line or a recording medium on which the recipe is recorded. Also, an existing recipe that has already been installed in the processing device may be directly modified by operating the input / output device 122 provided in the existing processing device.

[0144] In the above-mentioned embodiment, an example of forming a film using a batch-type processing apparatus that processes multiple substrates at a time has been described. The present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a single-wafer processing apparatus that processes one or several substrates at a time. In addition, in the above-mentioned embodiment, an example of forming a film using a processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a processing apparatus having a cold-wall type processing furnace.

[0145] When using these processing apparatuses, each process can be performed according to the same process procedures and under the same process conditions as in the above-mentioned aspects and modifications, and the same effects as in the above-mentioned aspects and modifications can be obtained.

[0146] The above-mentioned aspects and modifications may be used in appropriate combination. The processing procedures and processing conditions in such a case may be the same as those of the above-mentioned aspects and modifications. [Explanation of symbols]

[0147] 200 wafers (substrates)

Claims

1. (a) supplying a first film-forming agent to a substrate having a first underlayer and a second underlayer on a surface thereof to form a first film containing a first element and a second element on a surface of the first underlayer; (b) supplying a modifier to the substrate to adsorb at least a part of a molecular structure of a molecule constituting the modifier onto the surface of the first film formed on the surface of the first base, thereby forming an inhibitor layer; (c) supplying a second film-forming agent to the substrate on which the inhibitor layer is formed on the surface of the first film, thereby forming a second film containing the first element and the second element on a surface of the second base; The processing method according to claim 1,

2. 2. The method of claim 1, wherein the first film is an oxide film and the second film is an oxide film.

3. 2. The method of claim 1, wherein the first element is silicon and the second element is oxygen.

4. 4. The method of claim 3, wherein the first film is a silicon oxide film, a silicon oxycarbide film, or a silicon oxycarbonitride film, and the second film is a silicon oxide film, a silicon oxycarbonitride film, or a silicon oxycarbonitride film.

5. 2. The method according to claim 1, wherein the first film and the second film are made of the same material.

6. In step (a), a first source material and a first oxidizing agent are supplied to the substrate as the first film forming agent; 2. The processing method according to claim 1, wherein in (c), a second source material and a second oxidizing agent are supplied to the substrate as the second film forming agent.

7. In (a), a cycle including the steps of (a1) supplying the first source material to the substrate and (a2) supplying the first oxidant to the substrate is performed a predetermined number of times; 7. The processing method according to claim 6, wherein in (c), a cycle including the steps of (c1) supplying the second source to the substrate and (c2) supplying the second oxidant to the substrate is performed a predetermined number of times.

8. In at least one of (a1) and (a2), a first catalyst is further supplied; The method according to claim 7, further comprising the step of: (c1) or (c2) further comprising the step of supplying a second catalyst.

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

10. 9. The processing method according to claim 6, wherein the first source material and the second source material are the same substance, and the first oxidant and the second oxidant are the same substance.

11. 9. The method of claim 8, wherein the first feedstock and the second feedstock 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.

12. The processing method according to any one of claims 1 to 5, wherein the thickness of the first film is set to be equal to or smaller than 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 method according to any one of claims 1 to 5, wherein (a) is carried out under processing conditions in which the film formation rate is lower than that of (c).

14. 6. The method according to claim 1, wherein the temperatures of the substrate in (a), (b) and (c) are the same.

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

16. The method according to any one of claims 1 to 5, further comprising the step of: (d) removing the first film by supplying an etching agent to the substrate after the second film is formed on the surface of the second base.

17. The processing method according to any one of claims 1 to 5, further comprising the step of: (e) supplying a third film forming agent to the substrate after the second film is formed, thereby forming a third film on the second film.

18. 6. The processing method according to claim 1, wherein the first underlayer includes an insulating film, and the second underlayer includes at least one of a semiconductor substrate, a film of a simple semiconductor element, and a film of a simple metal element.

19. (a) supplying a first film-forming agent to a substrate having a first underlayer and a second underlayer on a surface thereof to form a first film containing a first element and a second element on a surface of the first underlayer; (b) supplying a modifier to the substrate to adsorb at least a part of a molecular structure of a molecule constituting the modifier onto the surface of the first film formed on the surface of the first base, thereby forming an inhibitor layer; (c) supplying a second film-forming agent to the substrate on which the inhibitor layer is formed on the surface of the first film, thereby forming a second film containing the first element and the second element on a surface of the second base; A method for manufacturing a semiconductor device having the above structure.

20. a first film forming agent supply system that supplies a first film forming agent to the substrate; a modifier supply system for supplying a modifier to the substrate; a second film forming agent supply system that supplies a second film forming agent to the substrate; a control unit configured to be capable of controlling the first film-forming agent supply system, the modifier supply system, and the second film-forming agent supply system to perform the following processes: (a) a process of supplying the first film-forming agent to a substrate having a first underlayer and a second underlayer on a surface of the first underlayer, thereby forming a first film containing a first element and a second element on the surface of the first underlayer; (b) a process of supplying the modifier to the substrate, thereby adsorbing at least a part of a molecular structure of a molecule constituting the modifier on the surface of the first film formed on the surface of the first underlayer, thereby forming an inhibitor layer; and (c) a process of supplying the second film-forming agent to the substrate on which the inhibitor layer has been 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 underlayer. A processing device having

21. (a) supplying a first film-forming agent to a substrate having a first underlayer and a second underlayer on a surface thereof to form a first film including a first element and a second element on a surface of the first underlayer; (b) supplying a modifier to the substrate to adsorb at least a part of a molecular structure of a molecule constituting the modifier onto the surface of the first film formed on the surface of the first base, thereby forming an inhibitor layer; (c) supplying a second film-forming agent to the substrate on which the inhibitor layer is formed on the surface of the first film, thereby forming a second film containing the first element and the second element on a surface of the second base; A program that causes a processing device to execute the above by a computer.

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