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

Abstract

The invention relates to a substrate processing method, a semiconductor device manufacturing method, a recording medium, and a substrate processing apparatus. The present invention addresses the problem of providing a technique capable of suppressing adhesion of by-products caused by a reaction. The substrate processing method includes a step of sequentially performing (a), (b), and (c) a predetermined number of times to form a film containing an element contained in a raw material gas and an element contained in a reaction gas on a substrate, in which (a) is a step of supplying a first gas containing NH-to the substrate, (b) is a step of supplying a second gas containing NH-to the substrate, and (c) is a step of supplying a third gas containing NH-to the substrate. (b) a step for supplying the raw material gas to the substrate; and (c) a step for supplying the reaction gas to the substrate.

Description

Technical Field

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

[0002] As one of the steps in the manufacturing process of a semiconductor device, a process of forming a film on a substrate is sometimes performed (for example, see Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2008-124184 Summary of the invention

[0006] Problems to be solved by the invention

[0007] The present invention provides a technology capable of suppressing the adhesion of by-products caused by a reaction.

[0008] Means for solving problems

[0009] According to one embodiment of the present invention, there is provided a technique comprising the step of performing (a), (b) and (c) in sequence a predetermined number of times to form a film containing an element contained in a raw material gas and an element contained in a reaction gas on a substrate, wherein:

[0010] (a) a step of supplying a first gas containing NH − to the substrate;

[0011] (b) a step of supplying the raw material gas to the substrate;

[0012] (c) is a step of supplying the reaction gas to the substrate.

[0013] Effects of the Invention

[0014] According to the present invention, adhesion of by-products caused by the reaction can be suppressed. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 (a) is a schematic diagram of a vertical processing furnace of a substrate processing device preferably used in one embodiment of the present invention, and is a diagram showing a processing furnace 202 portion in a longitudinal sectional view;

[0016] Figure 1 (b) is a longitudinal section view showing the airtight sealing Figure 1 FIG. 1 is a diagram of a furnace cover having an opening at the lower end of the manifold 209 shown in (a).

[0017] Figure 2This is a schematic diagram of a vertical processing furnace of a substrate processing device preferably used in one embodiment of the present invention. Figure 1 The AA line cross-sectional view of (a) shows a portion of the processing furnace 202 .

[0018] Figure 3 1 is a schematic diagram of the configuration of a controller 121 of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a diagram showing a control system of the controller 121 in the form of a block diagram.

[0019] Figure 4 It is a diagram showing a substrate processing flow in one embodiment of the present invention.

[0020] Figure 5 It is a diagram showing a substrate processing procedure in one embodiment of the present invention.

[0021] Figure 6 (a) is a diagram showing a supply sequence of a modifier in one embodiment of the present invention, Figure 6 (b) is a diagram showing a raw material supply sequence in one embodiment of the present invention, Figure 6 (c) is a diagram showing the order of supplying the oxidant in one embodiment of the present invention, Figure 6 (d) is a diagram showing the raw material supply sequence in one embodiment of the present invention, Figure 6 (e) is a diagram showing the raw material supply sequence in one embodiment of the present invention, Figure 6 (f) is a diagram showing the order of supplying the oxidizing agent in one embodiment of the present invention.

[0022] Figure 7 (a) is a diagram showing a supply sequence of a modifier in one embodiment of the present invention, Figure 7 (b) is a diagram showing the order of supplying the modifying agent in another embodiment of the present invention, Figure 7 (c) is a diagram showing a supply sequence of a modifying agent in another embodiment of the present invention, Figure 7 (d) is a diagram showing a supply sequence of a modifying agent in another embodiment of the present invention, Figure 7 (e) is a diagram showing a supply sequence of a reforming agent according to another embodiment of the present invention.

[0023] Figure 8 (a) is a diagram schematically showing film formation and adsorption in a concave structure in an embodiment, Figure 8 (b) is a diagram schematically showing film formation and adsorption in a concave structure in a comparative example.

[0024] Fig. 9 It is a figure which shows an Example and a comparative example.

[0025] Description of Reference Numerals

[0026] 200 wafers (substrate) DETAILED DESCRIPTION

[0027] <One embodiment of the present invention>

[0028] The following mainly refers to Figure 1 (a) and Figure 1 (b) and Figure 2 to Figure 5 One embodiment of the present invention is described. It should be noted that the drawings used in the following description are schematic, and the relationship between the dimensions of the elements shown in the drawings, the ratio of the elements, etc. may not be consistent with reality. In addition, the relationship between the dimensions of the elements, the ratio of the elements, etc. may not be consistent between multiple drawings.

[0029] (1) Configuration of substrate processing apparatus

[0030] like Figure 1 (a) and Figure 1 As shown in (b) of FIG. 2 , the processing furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is vertically installed by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) the gas by heat.

[0031] On the inner side of the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO) or silicon carbide (SiC), and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS), and is formed into a cylindrical shape with an upper end and a lower end open. The upper end of the manifold 209 is engaged with the lower end of the reaction tube 203, and is configured to support the reaction tube 203. An O-ring 220a as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically in the same manner as the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing container (reaction container). A processing chamber 201 is formed in the hollow portion of the cylinder of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. The wafer 200 is processed in the processing chamber 201 .

[0032] In the processing chamber 201, nozzles 249a to 249c as the first to third supply parts are respectively provided in a manner penetrating the side wall of the manifold 209. The nozzles 249a to 249c are also referred to as the first to third nozzles, respectively. The nozzles 249a to 249c are made of, for example, a heat-resistant material such as quartz or SiC. Gas supply pipes 232a to 232c are respectively connected to the nozzles 249a to 249c. The nozzles 249a to 249c are different nozzles, and the nozzles 249a and 249c are respectively provided adjacent to the nozzle 249b.

[0033] On the gas supply pipes 232a to 232c, mass flow controllers (MFC) 241a to 241c as flow controllers (flow control units) and valves 243a to 243c as on-off valves are respectively provided in sequence from the upstream side of the gas flow. Gas supply pipes 232d to 232f are respectively connected to the downstream side of the gas supply pipes 232a to 232c than the valves 243a to 243c. On the gas supply pipes 232d to 232f, MFCs 241d to 241f and valves 243d to 243f are respectively provided in sequence from the upstream side of the gas flow. The gas supply pipes 232a to 232f are made of metal materials such as SUS, for example.

[0034] like Figure 2 As shown, the nozzles 249a to 249c are respectively arranged in a circular ring-shaped space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, so as to stand up from the lower part of the inner wall of the reaction tube 203 along the upper part toward the upper side of the arrangement direction of the wafer 200. That is, the nozzles 249a to 249c are respectively arranged in a region that horizontally surrounds the wafer arrangement region on the side of the wafer arrangement region where the wafers 200 are arranged in a manner along the wafer arrangement region. In a plan view, the nozzle 249b is arranged so as to face the exhaust port 231a described later on a straight line with the center of the wafer 200 carried into the processing chamber 201 sandwiched therebetween. The nozzles 249a and 249c are arranged so as to sandwich a straight line L passing through the center of the nozzle 249b and the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer periphery of the wafer 200). The straight line L is also a straight line passing through the center of the nozzle 249b and the wafer 200. That is, the nozzle 249c may be arranged on the opposite side of the nozzle 249a with the straight line L sandwiched therebetween. The nozzles 249a and 249c are arranged line-symmetrically with the straight line L as the axis of symmetry. Gas supply holes 250a to 250c for supplying gas are respectively provided on the side surfaces of the nozzles 249a to 249c. The gas supply holes 250a to 250c are respectively opened in a manner opposite to (facing) the exhaust port 231a when viewed from above, and can supply gas to the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the bottom to the top of the reaction tube 203.

[0035] A reforming agent (reforming gas) is supplied into the processing chamber 201 from the gas supply pipe 232 a via the MFC 241 a , the valve 243 a , and the nozzle 249 a .

[0036] A raw material (raw material gas) is supplied from the gas supply pipe 232b through the MFC 241b, the valve 243b, and the nozzle 249b into the processing chamber 201. The raw material is used as one of the film-forming agents.

[0037] An oxidizing agent (oxidizing gas) is supplied from the gas supply pipe 232c through the MFC 241c, the valve 243c, and the nozzle 249c into the processing chamber 201. The oxidizing agent is used as one of the film-forming agents.

[0038] Inert gas is supplied from gas supply pipes 232d to 232f into the processing chamber 201 via MFCs 241d to 241f, valves 243d to 243f, gas supply pipes 232a to 232c, and nozzles 249a to 249c. The inert gas functions as a purge gas, a carrier gas, a dilution gas, and the like.

[0039] The reformer supply system (reforming gas supply system) is mainly composed of the gas supply pipe 232a, MFC241a, and valve 243a. The raw material supply system (raw material gas supply system) is mainly composed of the gas supply pipe 232b, MFC241b, and valve 243b. The oxidant supply system (oxidizing gas supply system) is mainly composed of the gas supply pipe 232c, MFC241c, and valve 243c. The inert gas supply system is mainly composed of the gas supply pipes 232d to 232f, MFC241d to 241f, and valves 243d to 243f.

[0040] Any one or all of the above-mentioned various supply systems may also be configured as an integrated supply system 248 in which valves 243a to 243f, MFCs 241a to 241f, etc. are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232f, and is configured so that the supply operation of various substances (various gases) in the gas supply pipes 232a to 232f, i.e., the opening and closing operation of the valves 243a to 243f, the flow rate adjustment operation based on the MFCs 241a to 241f, etc., is controlled by the controller 121 described later. The integrated supply system 248 is configured as an integrated unit of an integral type or a split type, and can be mounted and disassembled relative to the gas supply pipes 232a to 232f, etc. as an integrated unit, and is configured so that the integrated supply system 248 can be maintained, replaced, and added as an integrated unit.

[0041] An exhaust port 231a is provided below the side wall of the reaction tube 203 to exhaust the atmosphere in the processing chamber 201. Figure 2As shown, the exhaust port 231a is provided at a position opposite (facing) to the nozzles 249a to 249c (gas supply holes 250a to 250c) sandwiching the wafer 200 in a plan view. The exhaust port 231a may also be provided along the lower part to the upper part of the side wall of the reaction tube 203, that is, along the wafer arrangement area. The exhaust port 231a is connected to the exhaust pipe 231. The exhaust pipe 231 is connected to a vacuum pump 246 as a vacuum exhaust device 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 regulation unit). The APC valve 244 is configured to open and close the valve in a state where the vacuum pump 246 is operated, so that the vacuum exhaust in the processing chamber 201 can be performed and the vacuum exhaust can be stopped. Furthermore, in a state where the vacuum pump 246 is operated, the valve opening is adjusted based on the pressure information detected by the pressure sensor 245, so that the pressure in the processing chamber 201 can be adjusted. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. It is also conceivable that a vacuum pump 246 is included in the exhaust system.

[0042] A sealing cover 219 as a furnace port cover body capable of hermetically closing the lower end opening of the manifold 209 is provided below the manifold 209. The sealing cover 219 is made of a metal material such as SUS and is formed into a disc shape. An O-ring 220b as a sealing member abutting against the lower end of the manifold 209 is provided on the upper surface of the sealing cover 219. A rotating mechanism 267 for rotating the wafer boat 217 described later is provided below the sealing cover 219. The rotating shaft 255 of the rotating mechanism 267 passes through the sealing cover 219 and is connected to the wafer boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217. The sealing cover 219 is configured to be lifted and lowered in the vertical direction by the wafer boat elevator 115 as a lifting mechanism provided outside the reaction tube 203. The boat elevator 115 is configured as a transport device (transport mechanism) that carries the wafer 200 into and out of the processing chamber 201 by raising and lowering the sealing cap 219 .

[0043] A rotating mechanism 267 for rotating a wafer boat 217 described later is provided below the sealing cover 219. A rotating shaft 255 of the rotating mechanism 267 penetrates the sealing cover 219 and is connected to the wafer boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217. The sealing cover 219 is configured to be raised and lowered in the vertical direction by a wafer boat elevator 115 as an elevating mechanism provided outside the reaction tube 203. The wafer boat elevator 115 is configured as a transport device (transport mechanism) that carries the wafer 200 into and out of the processing chamber 201 by raising and lowering the sealing cover 219.

[0044] A gate 219s as a furnace cover is provided below the manifold 209, which can hermetically seal the lower end opening of the manifold 209 when the sealing cover 219 is lowered and the wafer boat 217 is moved out of the processing chamber 201. The gate 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c as a sealing member abutting against the lower end of the manifold 209 is provided on the upper surface of the gate 219s. The opening and closing action (lifting action, rotation action, etc.) of the gate 219s is controlled by the gate opening and closing mechanism 115s.

[0045] The wafer boat 217 as a substrate support is configured to support a plurality of wafers 200, for example, 25 to 200 wafers 200, arranged in a horizontal posture and in a state where the centers are aligned with each other in a vertical direction and arranged in multiple layers, that is, arranged at intervals. The wafer boat 217 is made of a heat-resistant material such as quartz or SiC. A heat insulation plate 218 made of a heat-resistant material such as quartz or SiC is supported in multiple layers at the bottom of the wafer boat 217.

[0046] A temperature sensor 263 as a temperature detector is provided in the reaction tube 203. The temperature in the processing chamber 201 is adjusted to a desired temperature distribution by adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0047] like Figure 3 As shown, the controller 121 as a control unit (control unit) is configured as a computer having a CPU (Central Processing Unit; Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. RAM121b, a storage device 121c, and an I / O port 121d are configured to be able to exchange data with the CPU121a via an internal bus 121e. An input and output device 122 such as a touch panel is connected to the controller 121. In addition, an external storage device 123 can be connected to the controller 121. It should be noted that the substrate processing device can be configured to have one control unit or multiple control units. That is, one control unit can be used to control the processing sequence described later, or multiple control units can be used to control the processing sequence described later. In addition, multiple control units can be configured as a control system interconnected by a wired or wireless communication network, or the control system as a whole can be used to control the processing sequence described later. When the term "control unit" is used in this specification, it includes not only one control unit but also a plurality of control units and a control system including a plurality of control units.

[0048] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. A control program for controlling the actions of the substrate processing device, a process recipe recording the steps and conditions of the substrate processing described later, etc. are stored in a readable manner in the storage device 121c. The process recipe is a combination of the controller 121 to enable the substrate processing device to perform the various steps of the substrate processing described later, and to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are collectively referred to as a program. In addition, the process recipe is also referred to as a process program. In this specification, when the term "program" is used, sometimes only the process is included alone, sometimes only the control program is included alone, or sometimes both are included. RAM121b is configured as a memory area (work area) for temporarily holding programs, data, etc. read by CPU121a.

[0049] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241f, valves 243a to 243f, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, gate opening and closing mechanism 115s, etc.

[0050] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in accordance with an input of an operation command from the input / output device 122. The CPU 121a is configured to control, according to the contents of the read recipe, flow rate adjustment operations of various substances (various gases) by the MFCs 241a to 241f, opening and closing operations of the valves 243a to 243f, opening and closing operations of the APC valve 244 and pressure adjustment operations by the APC valve 244 based on the pressure sensor 245, start and stop of the vacuum pump 246, temperature adjustment operations of the heater 207 by the temperature sensor 263, rotation of the wafer boat 217 by the rotating mechanism 267 and rotation speed adjustment operations, lifting and lowering operations of the wafer boat 217 by the wafer boat elevator 115, opening and closing operations of the gate 219s by the gate opening and closing mechanism 115s, and the like.

[0051] The controller 121 can be configured by installing the above-mentioned program stored in the external storage device 123 on a computer. The external storage device 123 includes, for example, a disk such as an HDD, an optical disk such as a CD, an optical disk such as an MO, a semiconductor memory such as a USB memory, and an SSD. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, they are collectively referred to as recording media. In this specification, when the term recording medium is used, sometimes only the storage device 121c is included alone, sometimes only the external storage device 123 is included alone, or sometimes both are included. In addition, the program can be provided to the computer using a communication line such as the Internet or a dedicated line instead of the external storage device 123.

[0052] (2) Substrate processing step

[0053] Regarding an example of a process sequence for forming a film on a wafer 200 as a substrate as one of the steps in the manufacturing process of a semiconductor device using the substrate processing apparatus described above, the main steps are as follows: Figure 4 and Figure 5 In the following description, the operations of the various components constituting the substrate processing apparatus are controlled by the controller 121. Figure 4 The substrate processing flow includes wafer filling, pressure adjustment and temperature adjustment, film formation, post-purge and wafer removal.

[0054] The substrate processing step (substrate processing method) of this embodiment includes the steps of performing (a), (b) and (c) in sequence for a predetermined number of times to form a film containing the elements contained in the raw material gas and the elements contained in the reaction gas on the wafer 200, wherein:

[0055] (a) is a process of supplying a first gas containing NH − to the wafer 200;

[0056] (b) is a process of supplying raw material gas to the wafer 200;

[0057] (c) is a step of supplying a reaction gas to the wafer 200 .

[0058] exist Figure 5 In the processing sequence shown, a cycle including step A, step B and step C is performed a specified number of times (n times, n is an integer greater than 1), wherein step A is a step of supplying a modifier as a first gas to the chip 200 to form an adsorption layer on the chip 200 including the modifier physically adsorbed on the surface of the chip 200; step B is a step of supplying a raw material including a first element to the chip 200 to react the raw material with the surface of the chip 200 to form a first layer including the first element on the chip 200; and step C is a step of supplying an oxidant to the chip 200 to react the oxidant with the first layer to modify the first layer into a second layer including the first element and oxygen.

[0059] It should be noted that in Figure 5 In the processing sequence shown, the adsorption layer suppresses adsorption of byproducts generated when forming the first layer to at least one of the first layer and the surface of the wafer 200. The first layer may be a film that does not contain the element contained in the modifier.

[0060] In this specification, for convenience, the above-mentioned processing order may be shown as follows. The same reference numerals are also used in the following description of modified examples, other aspects, etc.

[0061] (modifier→raw material→oxidant)×n

[0062] The term "wafer" used in this specification may refer to the wafer itself or to a laminate of a wafer and a predetermined layer or film formed on its surface. The term "surface of the wafer" used in this specification may refer to the surface of the wafer itself or to the surface of a predetermined layer, etc. formed on the wafer. When it is stated in this specification that "a predetermined layer is formed on the wafer", it may refer to directly forming the predetermined layer on the surface of the wafer itself or to forming the predetermined layer on the layer, etc. formed on the wafer. The use of the term "substrate" in this specification is also synonymous with the use of the term "wafer".

[0063] The term "agent" used in this specification includes at least one of a gaseous substance and a liquid substance. A liquid substance includes a mist substance. That is, each of the modifier and the film-forming agent (raw material, oxidant) may include a gaseous substance, a liquid substance such as a mist substance, or both.

[0064] (Wafer filling and wafer boat loading)

[0065] When a plurality of wafers 200 are loaded into the wafer boat 217 (wafer filling), the gate 219s is moved by the gate opening and closing mechanism 115s, and the lower end opening of the manifold 209 is opened (gate opening). Figure 1 As shown in (a) in the figure, the wafer boat 217 supporting a plurality of wafers 200 is lifted by the wafer boat elevator 115 and moved into the processing chamber 201 (wafer boat loading). In this state, the sealing cover 219 is in a state of sealing the lower end of the manifold 209 via the O-ring 220b. It should be noted that a concave structure such as a trench and a hole is formed on the surface of the wafer 200. The aspect ratio of the concave structure, that is, the ratio calculated by (the depth of the internal space of the concave structure) / (the width of the internal space of the concave structure), is, for example, greater than 10.

[0066] (Pressure regulation and temperature regulation)

[0067] After the wafer boat is loaded, vacuum exhaust (decompression exhaust) is performed by the vacuum pump 246 so that the space in the processing chamber 201, that is, the space where the wafer 200 is present, becomes a desired pressure (vacuum degree). At this time, the pressure in 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. In addition, the heater 207 is used to heat the wafer 200 in the processing chamber 201 so that it becomes a desired processing temperature. At this time, the power supply status of the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the temperature distribution in the processing chamber 201 becomes a desired temperature distribution. In addition, the rotation of the wafer 200 by the rotation mechanism 267 is started. The exhaust in the processing chamber 201, the heating and rotation of the wafer 200 are all continuously performed until the processing of the wafer 200 is completed.

[0068] (Film Forming)

[0069] Afterwards, the following steps A to C are performed in sequence.

[0070] [Step A]

[0071] In this step, a modifying agent is supplied to the wafer 200 in the processing chamber 201 .

[0072] Specifically, valve 243a is opened to allow the modifier to flow into the gas supply pipe 232a. The modifier is flow-regulated by MFC 241a, supplied into the processing chamber 201 through nozzle 249a, and exhausted from exhaust port 231a. At this time, the modifier is supplied to the wafer 200 (modifier supply). The modifier is sometimes supplied in a state diluted with a diluent gas such as an inert gas. In addition, at this time, valves 243d to 243f may be opened to supply inert gases into the processing chamber 201 through each of nozzles 249a to 249c.

[0073] By supplying a modifier to the wafer 200 under the conditions described below, so that the modifier is physically adsorbed on the surface of the wafer 200, an adsorption layer including the modifier physically adsorbed on the surface of the wafer 200 can be formed on the wafer 200. As a result of the formation of the adsorption layer, a portion of the adsorption sites existing on the surface of the wafer 200 are covered by the adsorption layer, and another portion of the adsorption sites are not covered by the adsorption layer and are exposed. Here, the adsorption sites existing on the surface of the wafer 200 include, for example, hydroxyl groups (OH groups) that block the surface of the wafer 200. In addition, since the modifier includes an organic compound as described below, at least a portion of the surface of the adsorption layer can be blocked by hydrocarbon groups or the like.

[0074] The thickness of the adsorption layer is preferably less than 1 molecular layer. That is, the adsorption layer preferably contains a modifier adsorbed in a manner that discontinuously covers the surface of the chip 200. As a result, a portion of the adsorption sites (OH groups) present on the surface of the chip 200 can be reliably exposed. However, at this stage, the modifier may be physically adsorbed on the surface of the chip 200 in advance so that the thickness of the adsorption layer is greater than 1 molecular layer (that is, the surface of the chip 200 is covered with a continuous layer in advance), and in step A2 described later, a portion of the modifier contained in the adsorption layer is removed from the surface of the chip 200, thereby forming an adsorption layer with a thickness of less than 1 molecular layer.

[0075] It should be noted that in this step, an adsorption layer is formed on at least the surface near the opening (particularly the side wall near the opening) of the inner surface of the concave structure formed on the surface of the wafer 200. In addition, as described later, in this step, it is more preferred to further form an adsorption layer on the bottom surface and the side wall of the inner surface of the concave structure. In other words, the adsorption layer is formed on a portion of the exposed surface (also referred to as an adsorption site, an exposed portion) of the surface of the wafer 200. Here, the portion of the exposed surface is, for example, at least the surface near the opening (particularly the side wall near the opening) of the inner surface of the concave structure.

[0076] After the adsorption layer is formed on the wafer 200 , the valve 243 a is closed to stop the supply of the modifying agent into the processing chamber 201 .

[0077] After the supply of the modifying agent to the wafer 200 is completed (after stopping), as Figure 5 As shown, it is preferred to perform step A2 in which the process chamber 201 is evacuated while the supply of the modifier to the process chamber 201 is stopped, and the gas remaining in the process chamber 201 is removed from the process chamber 201. By continuing step A2, a part of the modifier contained in the adsorption layer can be removed from the surface of the wafer 200 (detached), and the density (thickness) of the adsorption layer formed on the wafer 200 can be adjusted to a desired density (thickness). That is, in step A2, the process chamber 201 can be continuously evacuated until the thickness of the adsorption layer reaches a desired density. As a result, the thickness of the first layer formed per cycle can be optimized, and the formation rate of the film on the wafer 200 can be adjusted to a relatively large desired size. In step A2, it is preferred to set the exhaust conditions in the process chamber 201, i.e., the exhaust time, the exhaust speed, etc., so that the formation rate of the film formed on the wafer 200 becomes a desired size.

[0078] It should be noted that if Figure 5As shown in FIG. 2 , in step A2, preferably, valves 243d to 243f are opened to supply inert gas into the processing chamber 201 through nozzles 249a to 249c. That is, in step A2, it is preferred that the processing chamber 201 be evacuated while supplying inert gas to the wafer 200. In addition, it is preferred that, in step A2, as shown in FIG. Figure 6 As shown in (a) of FIG. 2 , a step of exhausting the processing chamber 201 while supplying an inert gas to the wafer 200 (inert gas purging step) and a step of exhausting the processing chamber 201 while stopping the supply of the inert gas (vacuum purging step) may also be performed. In addition, preferably, in step A2, a purging cycle may be performed multiple times, and the purging cycle includes (not performed simultaneously): a step of exhausting the processing chamber 201 while supplying an inert gas to the wafer 200; and a step of exhausting the processing chamber 201 while stopping the supply of the inert gas.

[0079] By performing step A2 as described above, part of the modifier physically adsorbed on the surface of the wafer 200 can be removed more efficiently from the surface of the wafer 200, and the density (thickness) of the adsorption layer formed on the wafer 200 can be more reliably adjusted to a desired density (thickness). As a result, for example, the thickness of the first layer formed per cycle can be further optimized, and the film can be formed on the wafer 200 at a higher rate.

[0080] As the treatment conditions in supplying the reforming agent in step A, the following can be exemplified:

[0081] Modifier supply flow rate (excluding dilution gas): 0.01 to 10 g / min, more preferably 0.1 to 5 g / min

[0082] Dilution gas supply flow rate: 100 to 100,000 sccm, more preferably 1,000 to 50,000 sccm Modifier supply time: 1 to 600 seconds, more preferably 10 to 300 seconds

[0083] Inert gas supply flow rate (per gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm

[0084] Treatment temperature: 200-500°C, more preferably 200-350°C

[0085] Treatment pressure: 100-10000Pa, more preferably 100-1000Pa.

[0086] It should be noted that the expression of a numerical range such as "100 to 100,000 sccm" in this specification means that the lower limit and the upper limit are included in the range. Therefore, for example, "100 to 100,000 sccm" means "above 100 sccm and below 100,000 sccm". The same applies to other numerical ranges. It should be noted that the so-called flow rate of 0 sccm means that the supply of the substance is not implemented.

[0087] The processing conditions in step A2 include:

[0088] Exhaust time: 1 to 600 seconds, more preferably 10 to 300 seconds

[0089] Inert gas supply flow rate (per gas supply pipe): 0 to 100,000 sccm, more preferably 0 to 50,000 sccm.

[0090] As a modifier, a gas containing an inorganic compound, a gas containing an organic compound, or a gas containing both an inorganic compound and an organic compound can be used. For example, a gas containing ammonia (NH3), hydrazine (N2H4), diazene (N2H2), etc. can be used as an inorganic compound. It should be noted that inorganic compounds are also referred to as materials without organic ligands. As a gas containing an organic compound, a gas selected from at least one of the groups containing amine compounds and organic hydrazine compounds can be used. As a gas containing an amine compound, a gas containing at least one of methylamine compounds such as monomethylamine, dimethylamine, and trimethylamine, ethylamine compounds such as monoethylamine, diethylamine, and triethylamine, and methylethylamine, methyldiethylamine, etc. can be used. As a gas containing an organic hydrazine compound, a gas containing at least one of methylhydrazine-based gases such as monomethylhydrazine, dimethylhydrazine, and trimethylhydrazine can be used. As a modifier, various gases containing NH- groups shown in the present invention can be used. As a modifier, one or more of them can be used. In addition, as a modifier, it is preferred to use a gas that is not easily chemically adsorbed on the surface of the wafer 200. In order to form an adsorption layer including a modifier physically adsorbed on the surface of the wafer 200 , for example, a gas that does not substantially chemically react with an adsorption site (OH group) on the surface of the wafer 200 can be preferably used.

[0091] In addition, as a modifier, a gas containing NH − and a gas containing an organic ligand and NH − may be supplied in an overlapping manner in at least one part of the supply period, or a gas containing NH − and a gas containing an organic ligand and NH − may be supplied in different periods.

[0092] As a modifier, a hydrazine-based inorganic compound and NH3 can be used. From the viewpoint of decomposition temperature, it is preferred to use more stable NH3. When the temperature in the reaction container (the temperature of the substrate) is a low temperature of about 100 to 200°C, a hydrazine-based inorganic compound can be used as a modifier. That is, by using a hydrazine-based inorganic compound, film formation under low temperature conditions can be performed.

[0093] In the process from the supply of the modifier and the raw material to the supply of the reaction gas following them, it is desirable to have no large temperature changes from the viewpoint of the manufacturing productivity of the semiconductor device. The use of NH3 enables film formation without significant temperature changes. However, when ozone (O3) is used as the reaction gas, it may be required to change from the temperature when the reforming gas is supplied to the temperature when the raw material gas / reaction gas is supplied. High-quality films can be formed if the time for each temperature adjustment is acceptable.

[0094] As the inert gas, rare gases such as nitrogen (N2), argon (Ar), helium (He), neon (Ne), and xenon (Xe) can be used. As the inert gas, one or more of them can be used. This is also the same in each step described later.

[0095] [Step B]

[0096] After step A is completed, the raw material is supplied to the wafer 200 in the processing chamber 201, that is, to the wafer 200 having the adsorption layer formed on the surface thereof.

[0097] Specifically, valve 243b is opened to allow the raw material to flow into gas supply pipe 232b. The raw material is flow-regulated by MFC241b, supplied into processing chamber 201 through nozzle 249b, and exhausted from exhaust port 231a. At this time, the raw material is supplied to wafer 200 (raw material supply). The raw material is sometimes supplied in a state diluted by a diluent gas such as an inert gas. In addition, at this time, valves 243d to 243f may be opened to supply inert gas into processing chamber 201 through each of nozzles 249a to 249c.

[0098] By supplying a raw material to the wafer 200 under the conditions described below, the raw material can be reacted with the surface of the wafer 200. As described below, the raw material includes molecules having a first element and a ligand bonded to the first element (hereinafter also referred to as raw material molecules). When the raw material reaches the surface of the wafer 200, it reacts with the adsorption sites (OH groups) exposed on the exposed surface of the wafer 200 that is not covered by the modified layer, that is, on the surface of the wafer 200. In other words, the molecules of the raw material gas are adsorbed on the exposed portion (adsorption site) existing on the surface of the wafer 200 that is not covered by the modified layer. The molecules of the raw material gas are adsorbed on other portions of the exposed portion where the adsorption layer is not formed. In the course of this reaction, the ligand is detached from the first element contained in the raw material, and the first element having an unbonded species due to the detachment of the ligand is chemically adsorbed (bonded) on the surface of the wafer 200. As this reaction proceeds, a first layer including the first element is formed on the wafer 200, that is, on the exposed surface (exposed portion) of the wafer 200 that is not covered by the adsorption layer.

[0099] It should be noted that, when the first layer is formed, predetermined by-products are generated. The by-products may include ligands that are separated from the first element due to the reaction between the raw material and the adsorption site exposed on the surface of the wafer 200. In addition, for example, the by-products may include molecules formed by the separation of a portion of the ligand from a molecule having the first element and a ligand bonded to the first element. It should be noted that the molecules formed by the separation of a portion of the ligand from a molecule having the first element and a ligand bonded to the first element may be generated by, for example, thermal decomposition of the raw material supplied to the processing chamber 201.

[0100] As described later, there are cases where the by-products contain organic ligands (organic matter), and the adsorption (adhesion) of the by-products on the surface of the film formed on the chip 200 and the residue of the by-products in the film are undesirable. The adsorption of the by-products on the surface of the film and the residue of the by-products in the film become the main factors for increasing the thickness of the film. Therefore, the adsorption amount and the residue of the by-products become uneven within the chip surface and the inner surface (inner wall) of the concave structure on the chip, thereby causing the film thickness uniformity of the film formed on the chip 200 within the chip surface and the step coverage of the film formed on the inner surface of the concave structure to deteriorate. In addition, the residue of the by-products in the film sometimes becomes the main factor for the reduction of the film quality caused by the increase of impurities from the by-products in the film.

[0101] With regard to such a problem, according to the present embodiment, the adsorption (attachment) of byproducts generated during the formation of the first layer to at least one of the first layer and the surface of the wafer 200 can be suppressed by the adsorption layer formed in advance in step A. Thus, it is possible to suppress the uncontrolled and uneven increase in the film thickness of the film formed on the wafer 200 due to the adsorption of byproducts, and suppress the residue of byproducts in the film.

[0102] One of the reasons why the adsorption of by-products to the first layer and the surface of the chip 200 can be suppressed is that the adsorption layer formed in step A reduces the exposure amount of the surface of the chip 200, that is, the amount of adsorption sites exposed on the surface of the chip 200 (density per unit area). As a result, the amount (degree) of reaction between the raw material and the surface of the chip 200 is properly controlled, and as a result, the amount of ligands detached from the first element, that is, the amount of by-products containing organic ligands, is reduced.

[0103] In addition, as one of the other reasons why the adsorption of byproducts to the surface of the first layer and the wafer 200 can be suppressed, it is considered that in addition to the reduction in the amount of byproducts generated when the first layer is formed as described above, the adsorption layer pre-formed in step A also appropriately covers and hides a portion of the surface of the wafer 200 in a manner that prevents the byproducts from adhering (physical adsorption), and the adsorption layer acts in a manner that suppresses the adsorption (adhesion) of byproducts generated when the first layer is formed to the surface of the first layer and the wafer 200. One of the reasons why the adsorption layer acts in a manner that suppresses the adsorption of byproducts to the surface of the first layer and the wafer 200 is that the modifier in a state of being physically adsorbed on the surface of the wafer 200 or a portion of the modifier detached from the surface of the wafer 200 preferentially adsorbs to the byproducts than to the surface of the first layer and the wafer 200, thereby suppressing the adsorption of byproducts to the first layer. By pre-forming the adsorption layer on the bottom surface and the side wall of the inner surface of the concave structure in step A, the adsorption of byproducts to the surface of the wafer 200 and the first layer can be sufficiently suppressed even near the bottom surface of the concave structure where the modifier is difficult to reach.

[0104] The by-products whose adsorption is suppressed are removed from the processing chamber 201 by exhaust. In addition, the reforming agent adsorbed on the by-products is removed from the processing chamber 201 by exhaust in this step and exhaust in a subsequent step.

[0105] After the formation of the first layer on the wafer 200 is completed, the valve 243 b is closed to stop the supply of the raw material into the processing chamber 201 .

[0106] After the supply of raw materials to the wafer 200 is completed (stopped), as Figure 4 As shown, it is preferred to perform step B2 of exhausting the process chamber 201 while stopping the supply of the raw material into the process chamber 201 to remove the gas remaining in the process chamber 201 from the process chamber 201 .

[0107] By performing step B2 , the atmosphere including the raw material remaining in the processing chamber 201 that has not reacted or has contributed to the formation of the first layer, and the byproducts whose adsorption is suppressed by the adsorption layer can be exhausted from the processing chamber 201 .

[0108] In addition, by performing step B2, the modifier contained in the adsorption layer, that is, the modifier physically adsorbed on the surface of the wafer 200 can be separated from the surface of the wafer 200. As a result, the modifier can be suppressed from remaining in the film formed on the wafer 200, and the film can be made into a film with a low impurity concentration caused by the modifier.

[0109] In addition, by performing step B2, the by-products attached to the adsorption layer can be removed from the surface of the wafer 200 together with the modifier contained in the adsorption layer, that is, the modifier physically adsorbed on the surface of the wafer 200. As a result, the by-products can be suppressed from remaining in the film formed on the wafer 200, and the film can be made to have excellent film thickness uniformity and step coverage within the wafer surface and a low impurity concentration caused by the by-products.

[0110] It should be noted that if Figure 5 As shown, in step B2, preferably, valves 243d to 243f are opened to supply inert gas into the processing chamber 201 through nozzles 249a to 249c. That is, in step B2, it is preferred that the processing chamber 201 be exhausted while supplying inert gas to the wafer 200. In addition, in step B2, as shown in FIG. Figure 6 As shown in (b) of FIG. 2 , the following steps may be performed: a step of exhausting the process chamber 201 while supplying an inert gas to the wafer 200; and a step of exhausting the process chamber 201 while stopping the supply of the inert gas. In addition, preferably, in step B2, the following purge cycle may be performed multiple times, the purge cycle including (performed non-simultaneously): a step of exhausting the process chamber 201 while supplying an inert gas to the wafer 200; and a step of exhausting the process chamber 201 while stopping the supply of the inert gas.

[0111] By performing step B2 as described above, a part of the modifier physically adsorbed on the surface of the wafer 200 can be removed from the surface of the wafer 200 more efficiently, and the above-mentioned various effects can be obtained more reliably.

[0112] As the processing conditions in the raw material supply in step B, the following can be exemplified:

[0113] Raw material supply flow rate (excluding dilution gas): 0.1 to 10 g / min, more preferably 0.5 to 5 g / min

[0114] Dilution gas supply flow rate: 100 to 100,000 sccm, more preferably 1,000 to 50,000 sccm

[0115] Raw material supply time: 10 to 600 seconds, more preferably 30 to 300 seconds

[0116] Inert gas supply flow rate (per gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm.

[0117] The other conditions can be the same as the treatment conditions in the supply of the reforming agent in step A.

[0118] The processing conditions in step B2 may be the same as those in step A2.

[0119] As a raw material, a gas containing molecules having a first element and a ligand bonded to the first element can be used. As the first element, metal elements can be cited, preferably transition metal elements, more preferably Group 4 elements such as zirconium (Zr), hafnium (Hf), and titanium (Ti). In addition, as the ligand bonded to the first element, an organic ligand can be cited, preferably a hydrocarbon group containing at least one selected from the group consisting of alkyl groups such as methyl, ethyl, propyl, and butyl, amino groups (at least NH- groups), alkylamino groups, cyclopentadienyl groups, cyclohexadienyl groups, and cycloheptatrienyl groups. More preferably, the first element, an amine group, and other groups are contained.

[0120] As a raw material containing Zr as the first element, for example, a gas containing at least any one selected from the group consisting of tetraethylmethylaminozirconium (Zr[N(CH3)C2H5]4), tetradiethylaminozirconium (Zr[N(C2H5)2]4), tetradimethylaminozirconium (Zr[N(CH3)2]4), Zr(MMP)4, Zr(O-tBu)4, and trisdimethylaminocyclopentadienylzirconium ((C5H5)Zr[N(CH3)2]3) can be used. As a raw material, one or more of these can be used.

[0121] In addition, as a raw material containing Hf as the first element, for example, a gas containing at least any one selected from the group consisting of tetraethylmethylaminohafnium (Hf[N(CH3)C2H5]4), tetradiethylaminohafnium (Hf[N(C2H5)2]4), tetradimethylaminohafnium (Hf[N(CH3)2]4), Hf(O-tBu)4, Hf(MMP)4, and trisdimethylaminocyclopentadienylhafnium ((C5H5)Hf[N(CH3)2]3) can be used. As a raw material, one or more of these can be used.

[0122] In addition, as a raw material containing Ti as the first element, for example, a gas containing at least any one selected from the group consisting of tetraethylmethylaminotitanium (Ti[N(CH3)C2H5]4), tetradiethylaminotitanium (Ti[N(C2H5)2]4), tetradimethylaminotitanium (Ti[N(CH3)2]4), Ti(O-tBu)4, Ti(MMP)4, and trisdimethylaminocyclopentadienyltitanium ((C5H5)Ti[N(CH3)2]3) can be used. As a raw material, one or more of these can be used.

[0123] [Step C]

[0124] After step B is completed, an oxidant, for example, is supplied as a reaction gas to the wafer 200 in the processing chamber 201 , that is, to the wafer 200 having the first layer including the first element formed on the surface thereof.

[0125] Specifically, valve 243c is opened to allow the oxidant to flow into the gas supply pipe 232c. The oxidant is flow-regulated by MFC241c, supplied into the processing chamber 201 through nozzle 249c, and exhausted from exhaust port 231a. At this time, the oxidant is supplied to the wafer 200 (oxidant supply). The oxidant is sometimes supplied in a state diluted with a diluent gas such as an inert gas or other oxygen-containing gas. In addition, at this time, valves 243d to 243f may be opened to supply an inert gas into the processing chamber 201 through each of nozzles 249a to 249c.

[0126] By supplying an oxidant to the wafer 200 under the conditions described below, the oxidant reacts with the first layer, and the first layer is reformed (oxidized) into a second layer including the first element and oxygen (O).

[0127] It should be noted that by-products may be generated when the second layer is formed. The by-products may include ligands that are separated from the first layer due to the reaction between the oxidant and the first layer. The by-products may also include organic ligands (organic matter) as the by-products generated when the first layer is formed. The re-adsorption (re-adhesion) of the by-products to the second layer and the residue of the by-products in the film formed on the wafer 200 caused by the by-products are not ideal.

[0128] With regard to such a problem, according to the present method, the adsorption of by-products generated when forming the second layer to at least one of the second layer and the surface of the wafer 200 can be suppressed by the adsorption layer preformed in step A. This is considered to be because, similarly to step B, the adsorption layer preformed in step A appropriately covers and hides a portion of the surface of the wafer 200, and the adsorption layer acts in a manner that suppresses (hinders) the re-adsorption (re-adhesion) of by-products generated when forming the second layer to the second layer.

[0129] The byproducts whose re-adsorption is suppressed are removed by exhaust from the processing chamber 201. It is also considered that part of the byproducts whose adsorption to the second layer and the surface of the wafer 200 is suppressed is adsorbed (attached) to the adsorption layer.

[0130] After the formation of the second layer on the wafer 200 is completed, the valve 243 c is closed to stop the supply of the oxidant into the processing chamber 201 .

[0131] After the supply of the oxidant to the wafer 200 is completed (stopped), as Figure 4 As shown, it is preferable to perform step C2 of exhausting the process chamber 201 while stopping the supply of the oxidant into the process chamber 201 to remove the gas remaining in the process chamber 201 from the process chamber 201 .

[0132] By performing step C2 , the atmosphere including the oxidant remaining in the processing chamber 201 that has not reacted or has contributed to the formation of the second layer, and the byproducts whose adsorption is suppressed by the adsorption layer can be exhausted from the processing chamber 201 .

[0133] In addition, by performing step C2, the modifier contained in the adsorption layer, that is, the modifier physically adsorbed on the surface of the wafer 200 can be separated from the surface of the wafer 200. As a result, the modifier can be suppressed from remaining in the film formed on the wafer 200, and the film can be made into a film with a low concentration of impurities caused by the modifier.

[0134] In addition, by performing step C2, the by-products attached to the adsorption layer can be removed from the surface of the wafer 200 together with the modifier contained in the adsorption layer, that is, the modifier physically adsorbed on the surface of the wafer 200. As a result, the by-products can be suppressed from remaining in the film formed on the wafer 200, and the film can be formed into a film with excellent film thickness uniformity and step coverage within the wafer surface and a low concentration of impurities caused by the by-products.

[0135] It should be noted that if Figure 4 As shown, in step C2, preferably, valves 243d to 243f are opened to supply inert gas into the processing chamber 201 through nozzles 249a to 249c. That is, in step C2, it is preferred that the processing chamber 201 be exhausted while supplying inert gas to the wafer 200. In addition, in step C2, as shown in FIG. Figure 6As shown in (c) in FIG. 2 , a step of exhausting the processing chamber 201 while supplying an inert gas to the wafer 200; and a step of exhausting the processing chamber 201 while stopping the supply of the inert gas may also be performed. In addition, preferably, in step C2, the following purge cycle may be performed multiple times, and the purge cycle includes (performed non-simultaneously): a step of exhausting the processing chamber 201 while supplying an inert gas to the wafer 200; and a step of exhausting the processing chamber 201 while stopping the supply of the inert gas.

[0136] By performing step C2 as described above, a part of the modifier physically adsorbed on the surface of the wafer 200 can be removed from the surface of the wafer 200 more efficiently, and the above-mentioned various effects can be obtained more reliably.

[0137] As the treatment conditions in the supply of the oxidizing agent in step C, the following can be exemplified:

[0138] Oxidant supply flow rate: 100 to 100,000 sccm, more preferably 1,000 to 10,000 sccm Oxidant supply time: 10 to 600 seconds, more preferably 30 to 300 seconds

[0139] Inert gas supply flow rate (per gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm.

[0140] The other conditions can be the same as the treatment conditions in the supply of the reforming agent in step A.

[0141] The processing conditions in step C2 can be the same as those in step A2.

[0142] As an oxidant, for example, a gas containing oxygen (O) and a gas containing oxygen (O) and hydrogen (H) can be used. As a gas containing O and H, for example, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, hydrogen (H2) gas + oxygen (O2) gas, H2 gas + ozone (O3) gas, etc. can be used. As a gas containing O, for example, oxygen (O2) gas, ozone (O3) gas, etc. can be used. O3 can be generated from O2 gas, for example, by an ozone generator. Therefore, the nozzle from the ozone generator releases a gas containing O2 and O3. The O3 generated in this way is supplied to the processing container and the substrate. Specifically, the oxidant supply nozzle provides O2 gas + O3 gas. In addition, other nozzles can provide inactive gas, and the supply of inactive gas can prevent O3 gas from entering the nozzle. In the case where the oxidant supply nozzle does not supply both the oxidant and the inactive gas, the oxidant supply nozzle and other nozzles supply O3, O2, and inactive gas to the processing container and the substrate.

[0143] It should be noted that, in this specification, the description of two gases such as "H2 gas + O2 gas" refers to a mixed gas of H2 gas and O2 gas. When supplying a mixed gas, the two gases can be mixed (pre-mixed) in a supply pipe and then supplied to the processing chamber 201, or the two gases can be supplied to the processing chamber 201 from different supply pipes and mixed (post-mixed) in the processing chamber 201.

[0144] [Number of times of implementation]

[0145] By performing the above-mentioned steps A to C non-simultaneously, i.e., asynchronously, for a predetermined number of times (n times, n being an integer greater than or equal to 1 or 2), a film containing the first element and O (an oxide film containing the first element) can be formed on the wafer 200, i.e., on the surface of the wafer 200 including the inner surface of the concave structure formed on the surface of the wafer 200. The above-mentioned cycle is preferably repeated a plurality of times. That is, it is preferred that the thickness of the second layer formed in each cycle is thinner than the desired thickness, and the above-mentioned cycle is repeated a plurality of times until the thickness of the oxide film formed by stacking the second layer reaches the desired thickness.

[0146] (Post-purge and atmospheric pressure recovery)

[0147] After the film is formed on the wafer 200, an inert gas is supplied from each of the nozzles 249a to 249c as a purge gas into the processing chamber 201, and the gas is exhausted from the exhaust port 231a. Thus, the processing chamber 201 is purged, and the gas remaining in the processing chamber 201, the reaction by-products, etc. are removed from the processing chamber 201 (post-purge). Then, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure recovery).

[0148] (Wafer boat unloading and wafer removal)

[0149] After that, the sealing cover 219 is lowered by the wafer boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the wafer boat 217 (wafer boat unloading). After the wafer boat is unloaded, the gate 219s is moved, and the lower end opening of the manifold 209 is sealed by the gate 219s via the O-ring 220c (gate closing). After the processed wafer 200 is carried out to the outside of the reaction tube 203, it is taken out from the wafer boat 217 (wafer taking out).

[0150] (3) Effects of this method

[0151] According to this aspect, one or more of the following effects can be obtained.

[0152] (a) When a cycle including steps A to C is performed a predetermined number of times, the quality of the film formed on the wafer 200 can be improved by suppressing the adsorption of byproducts generated when the first layer is formed to at least one of the first layer and the surface of the wafer 200 using the adsorption layer. For example, the uniformity of the film thickness within the wafer surface and the step coverage of the film formed on the wafer 200 can be improved. In addition, for example, the film formed on the wafer 200 can be made into a film with a low concentration of impurities caused by byproducts generated when the first layer is formed. As an example, the concentration of impurities contained in the film formed on the wafer 200 can be lower than the concentration of impurities contained in the film formed on the wafer 200 by performing a cycle including steps B and C without step A for the same predetermined number of times.

[0153] (b) When the cycle including steps A to C is performed a predetermined number of times, the quality of the film formed on the wafer 200 can be further improved by suppressing the adsorption of the by-products generated when the second layer is formed to at least one of the second layer and the surface of the wafer 200 using the adsorption layer. For example, the uniformity of the film thickness within the wafer surface and the step coverage of the film formed on the wafer 200 can be further improved. In addition, for example, the film formed on the wafer 200 can be made into a film with a lower concentration of impurities caused by the by-products generated when the second layer is formed.

[0154] (c) The modifier contained in the adsorption layer is physically adsorbed on the surface of the wafer 200, and therefore, it is easy to be separated from the surface of the wafer 200 during the cycle including steps A to C. As a result, the formation rate of the film formed on the wafer 200 can be adjusted to a desired level, and the productivity of the film forming process can be improved. In addition, the residue of the modifier in the film formed on the wafer 200 can be suppressed, so that the quality of the film can be improved.

[0155] For example, in step A, after supplying the modifier to the wafer 200, a part of the modifier contained in the adsorption layer can be removed from the surface of the wafer 200 by performing step A2 of exhausting the inside of the processing chamber 201. Thus, the density (thickness) of the adsorption layer formed on the wafer 200 can be adjusted to a desired density (thickness). As a result, the film can be formed on the wafer 200 at a desired rate. In addition, the remainder of the modifier in the film formed on the wafer 200 can be suppressed, and the film can be made into a film with a low concentration of impurities caused by the modifier.

[0156] In addition, for example, in step B, after supplying the raw material to the wafer 200, by performing step B2 of exhausting the inside of the processing chamber 201, the modifier contained in the adsorption layer can be separated from the surface of the wafer 200, thereby suppressing the modifier from remaining in the film formed on the wafer 200, and the film can be made into a film with a low concentration of impurities caused by the modifier. In addition, by removing the by-products attached to the adsorption layer from the surface of the wafer 200 together with the modifier contained in the adsorption layer, it is possible to suppress the by-products from remaining in the film formed on the wafer 200. As a result, the film can be made into a film with excellent uniformity and step coverage within the wafer surface, and with a low concentration of impurities caused by the by-products generated when the first layer is formed.

[0157] In addition, for example, in step C, after supplying the oxidant to the wafer 200, by performing step C2 of exhausting the inside of the processing chamber 201, the modifier contained in the adsorption layer can be separated from the surface of the wafer 200, thereby suppressing the modifier from remaining in the film formed on the wafer 200, and the film can be made into a film with a low concentration of impurities caused by the modifier. In addition, by removing the by-products attached to the adsorption layer from the surface of the wafer 200 together with the modifier contained in the adsorption layer, it is possible to suppress the by-products from remaining in the film formed on the wafer 200. As a result, the film can be formed into a film with excellent uniformity and step coverage within the wafer surface and a low concentration of impurities caused by by-products generated when the second layer is formed.

[0158] (d) In step A, a discontinuous adsorption layer (an adsorption layer having a thickness less than one molecular layer) is formed on the wafer 200 in advance, that is, a part of the adsorption sites (OH groups) existing on the surface of the wafer 200 is exposed in advance, thereby, in step B, the first element contained in the raw material can be bonded to the adsorption sites existing on the surface of the wafer 200. As a result, the film can be formed on the wafer 200 at a desired rate.

[0159] (e) The above-mentioned effect is particularly beneficial when a concave structure is formed on the surface of the wafer 200 and a film is to be formed on the inner surface of the concave structure.

[0160] This is because, when a film is to be formed on the inner surface of a concave structure formed on the surface of the wafer 200, the by-products generated in the concave structure will pass through the opening of the concave structure when being discharged from the concave structure, so there is a tendency for the exposure amount of the by-products to become larger near the opening of the concave structure compared to near the bottom of the concave structure. Therefore, by-products are easily adsorbed near the opening of the concave structure. As a result, compared with a film formed near the bottom of the concave structure, the film formed near the opening of the concave structure is likely to be a film with a high concentration of impurities caused by by-products and a film with an increased film thickness. In particular, when the concave structure has an aspect ratio of 10 or more, the problem described here will occur significantly.

[0161] According to this embodiment, as described above, the adsorption of byproducts generated during the formation of the first layer and the second layer to at least any one of the first layer, the second layer and the surface of the wafer 200 can be suppressed by the adsorption layer, so that the problem described here can be solved and the step coverage of the film formed on the inner surface of the concave structure formed on the wafer 200 can be improved. It should be noted that in step A, when the adsorption layer is formed on at least the bottom surface and the side wall of the inner surface of the concave structure, that is, when the adsorption layer is formed not only on the opening but also on the entire inner surface of the concave structure, the adsorption of byproducts can be suppressed not only on the opening of the concave structure but also on the bottom surface and the side wall. As a result, the step coverage of the film formed on the wafer 200 can be further improved, and a film with a low concentration of impurities caused by byproducts can be formed on the entire inner surface of the concave structure.

[0162] (f) The above-mentioned effects can also be obtained in the same manner when a predetermined substance (gaseous substance, liquid substance) is arbitrarily selected from the above-mentioned modifier group, raw material group, oxidant group, and inert gas group and used.

[0163] <Other aspects of the present invention>

[0164] The embodiments of the present invention have been specifically described above. However, the present invention is not limited to the embodiments described above, and various modifications can be made without departing from the gist of the present invention.

[0165] The raw material gas may be a gas containing at least one of an amino group and an organic ligand. NH- in the raw material gas containing an amino group is not easily adsorbed to the NH- terminal on the wafer 200, and the NH- on the wafer 200 acts as an inhibitor.

[0166] The constituent elements of the first layer do not include the constituent elements of the reformed gas. The second layer may be, for example, a film containing the first element of the raw material and oxygen derived from the oxidant.

[0167] For example, Figure 7As in (a) of FIG. 1 and the processing sequence shown below, in step A, a first reforming gas containing NH- is supplied to the wafer 200. The first reforming gas may be supplied without supplying the second reforming gas, and the first reforming gas does not contain an organic ligand. The first reforming gas may contain NH3, for example. Regarding the supply of NH3, since C, CH, etc. are not contained in the NH3 molecule, the possibility of C, CH, etc. from the first reforming gas remaining in the first layer deposited in the subsequent step can be reduced.

[0168] In addition, in step A, in addition to the first reforming gas, a second gas containing an organic ligand may be supplied as shown in the following processing sequence. It should be noted that the second gas may also contain an organic ligand and an NH- group. When the first reforming gas and the second gas are further supplied, for example, Figure 7 In step A, the first reforming gas may be supplied after the second reforming gas is supplied, as in step (b) and the processing sequence shown below. Figure 7 As in (c) and the processing sequence shown below, the second reforming gas may be supplied after the first reforming gas is supplied. Figure 7 As in (d) and the processing sequence shown below, the period during which the first reforming gas is supplied may partially overlap with the period during which the second reforming gas is supplied. Figure 7 As in the processing sequence shown in (e) and below, the first reformed gas and the second reformed gas can be supplied during the same period.

[0169] Furthermore, at least one of the first reformed gas and the second reformed gas may be supplied in a plurality of periods. Figure 7 (a) to Figure 7 Any of the conditions (e) in (e) can be satisfied. If a time-based split process is used, NH-capping is easily formed mainly on the upper side of the concave structure. This split process can reduce the supply amount in one pulse supply. In addition, in subsequent pulse supplies, NH3 can be supplied to the part where the NH- group has not been adsorbed (for example, the wafer 200 and the first layer in the film formation), and the same NH-capping can be formed near the opening of the concave structure of the wafer 200.

[0170] In step A, the first reforming gas is supplied to the processing chamber 201 and to the wafer 200 in the processing chamber 201 in a state where decomposition is suppressed, preferably in a state where no decomposition is performed (these states are referred to as "decomposition suppressed states"). For example, when the temperature of the reaction container is lower than the decomposition temperature of the reforming gas, the decomposition suppressed state is satisfied. This condition is satisfied when the temperature of the first reforming gas is lower than the decomposition temperature of the reforming gas. Figure 7 (a) to Figure 7 This can be satisfied in either case (e) or in the case of the split process.

[0171] Gases containing NH-, such as NH3, begin to decompose at a low temperature of 100°C, and almost all of NH3 is decomposed at around 400°C. If the reformed gas is supplied at a decomposition temperature of, for example, less than 400°C, a temperature slightly lower than 400°C, such as 350°C, the decomposition suppression state is satisfied. In addition to being related to temperature, the decomposition suppression state is also related to the flow rate, flow rate, pressure in the processing container, etc. of the supply gas. As an example, if the supply gas is supplied at a high flow rate, the time that the molecules in the flux of the supply gas are exposed to the above temperature can be shortened. As a result, the thermal energy imparted to the molecules of the supply gas is reduced, so that the amount of gas reaching the substrate surface before the molecules decompose is increased.

[0172] For example, the pressure condition in the processing chamber 201 can be set so that the pressure in step A is higher than the pressure in step B as shown in the following processing sequence. Figure 7 (a)~ Figure 7 This can be satisfied in any of the cases of (e), the split process, and the decomposition suppression state.

[0173] For example, the first supply conditions of the first reforming gas and the raw material gas may be set in such a manner that the supply amount (e.g., flow rate) of the first reforming gas becomes smaller than the supply amount (e.g., flow rate) of the raw material gas as in the following processing sequence. Figure 7 (a)~ Figure 7 This can be satisfied in any of the cases of (e), the split process, the decomposition suppression state, and the pressure condition.

[0174] For example, the second supply conditions of the first reforming gas and the reaction gas may be set such that the supply amount (e.g., flow rate) of the first reforming gas is smaller than the supply amount of the reaction gas, as in the following processing sequence. Figure 7 (a)~ Figure 7 Any of the conditions of (e), the split process, the decomposition suppression state, the pressure condition and the first supply condition can be satisfied.

[0175] For example, Figure 6 As in (d) in the above and the processing sequence shown below, in step B, the raw material supply cycle including the step of supplying the raw material to the wafer 200 and the step of exhausting the processing chamber 201 in a state where the supply of the raw material is stopped may be performed multiple times (m times, where m is an integer greater than 2). The processing conditions in these steps may be the same as the raw material supply described in the above method and the processing conditions in step B2.

[0176] (modifier→(raw material→exhaust gas)×m→oxidant)×n

[0177] If the continuous supply time of the raw material becomes longer, the thermal decomposition of the raw material proceeds, and sometimes the amount of by-products generated by the thermal decomposition increases. In order to suppress the increase in the amount of by-products caused by such thermal decomposition, it is preferred to shorten the continuous supply time of the raw material. In this method, by supplying the raw material in a time-sharing manner, the continuous supply time can be shortened, and the formation of the first layer is performed while suppressing the generation (increase) of by-products.

[0178] In addition, in such a case, each time the raw material supply cycle is repeated, the modifier contained in the adsorption layer can be separated from the surface of the wafer 200, and the residual modifier in the film can be further suppressed. In addition, each time the raw material supply cycle is performed, the by-products attached to the adsorption layer can be removed from the surface of the wafer 200 together with the modifier contained in the adsorption layer, and the residual by-products in the film can be further suppressed. As a result, the film formed on the wafer 200 can be made into a film with better film thickness uniformity and step coverage within the wafer surface, and a lower concentration of impurities caused by the modifier and by-products.

[0179] It should be noted that if Figure 6 As shown in (d) in FIG. 1 , in the exhaust step in the raw material supply cycle of this embodiment, it is preferred that the valves 243d to 243f be opened to supply an inert gas as a purge gas into the processing chamber 201 through the nozzles 249a to 249c.

[0180] In addition, for example, Figure 6 As in (e) and the processing sequence shown below, in the above-mentioned raw material supply cycle, a step of supplying a modifier to the wafer 200 may be further performed.

[0181] (modifier→(raw material→exhaust→modifier→exhaust)×m→oxidant)×n

[0182] or

[0183] (modifier→(raw material→exhaust→modifier)×m→oxidant)×n

[0184] When the raw material supply cycle is repeated as described above, the modifier contained in the adsorption layer will be separated from the surface of the wafer 200 each time it is repeated. As a result, there is a case where the modifier constituting the adsorption layer is insufficient. In this case, the insufficient modifier can be supplemented by supplying the modifier during the raw material supply cycle. As a result, the adsorption layer can more reliably suppress the adsorption of the by-products generated each time the raw material supply cycle is performed to at least one of the first layer and the surface of the wafer 200, and the film quality of the film formed on the wafer 200 can be further improved.

[0185] It should be noted that if Figure 6 As shown in (e) in the exhaust step in the raw material supply cycle of this embodiment, it is preferred to open valves 243d to 243f to supply an inert gas as a purge gas into the processing chamber 201 through nozzles 249a to 249c. In addition, in the raw material supply cycle of this embodiment, the exhaust step may not be performed after the step of supplying the modifier.

[0186] In addition, for example, Figure 6 As in (f) in the above and the processing sequence shown below, in step C, the oxidant supply cycle may be performed multiple times (m times, where m is an integer greater than 2), and the oxidant supply cycle includes: a step of supplying the oxidant to the wafer 200; and a step of exhausting the processing chamber 201 while stopping the supply of the oxidant. The processing conditions in these steps may be the same as the oxidant supply described in the above embodiment and the processing conditions in step C2.

[0187] (modifier→raw material→(oxidant→exhaust gas)×m)×n

[0188] In this case, each time the oxidant supply cycle is repeated, the modifier contained in the adsorption layer can be separated from the surface of the wafer 200, and the residual modifier in the film can be further suppressed. In addition, each time the oxidant supply cycle is performed, the by-products attached to the adsorption layer can be removed from the surface of the wafer 200 together with the modifier contained in the adsorption layer, and the residual by-products in the film can be further suppressed. As a result, the film formed on the wafer 200 can be made into a film with better film thickness uniformity and step coverage within the wafer surface, and a lower concentration of impurities caused by the modifier and by-products.

[0189] It should be noted that if Figure 6 As shown in (f) in FIG. 1 , in the exhaust step in the oxidant supply cycle of this embodiment, it is preferred that the valves 243d to 243f be opened to supply an inert gas as a purge gas into the processing chamber 201 through the nozzles 249a to 249c.

[0190] The process for each treatment is preferably prepared separately in advance according to the treatment content, and stored in the storage device 121c via the electric communication line and the external storage device 123. Moreover, when starting each treatment, it is preferred that the CPU 121a appropriately selects an appropriate process from the multiple processes stored in the storage device 121c according to the treatment content. In this way, films of various film types, composition ratios, film qualities, and film thicknesses can be formed with good reproducibility using one substrate processing device. In addition, the burden on the operator can be reduced, and each treatment can be started quickly while avoiding operational errors.

[0191] The above-mentioned process is not limited to the case of newly making, and can also be prepared by, for example, changing an existing process already installed in a substrate processing device. When changing a process, the changed process can also be installed in the substrate processing device via an electrical communication line or a recording medium recording the process. In addition, the input / output device 122 of the existing substrate processing device can be operated to directly change the existing process already installed in the substrate processing device.

[0192] In the above-mentioned method, an example of forming a film using a batch-type substrate processing device that processes a plurality of substrates at a time is described. The present invention is not limited to the above-mentioned method, and for example, it can also be appropriately applied to a case where a film is formed using a single-sheet substrate processing device that processes one or more substrates at a time. In addition, in the above-mentioned method, an example of forming a film using a substrate processing device having a hot-wall type processing furnace is described. The present invention is not limited to the above-mentioned method, and it can also be appropriately applied to a case where a film is formed using a substrate processing device having a cold-wall type processing furnace.

[0193] In the above-mentioned manner, an example is described in which an adsorption layer is formed on a part of the exposed portion of the concave structure formed on the wafer 200, and molecules of the raw material gas are adsorbed on other parts of the exposed portion. The present invention is not limited to the above-mentioned aspects. For example, a modifier may be supplied to the entire surface of the wafer 200, and then the raw material gas may be supplied to treat the wafer 200. In this way, the formation speed (film formation speed) of the film on the entire surface of the wafer 200 can be reduced, and a dense film can be formed. In this way, the film properties formed on the wafer 200 can be improved. Here, the film properties refer to either or both of the uniformity of the film thickness within the surface of the wafer 200 and the uniformity of the film thickness per wafer 200. Here, per wafer 200 refers to each processing in a single-wafer substrate processing device, and per wafer 200 in a case where multiple wafers are processed together in one substrate processing device. In particular, when the gas is supplied from the side of the wafer 200, the film properties per wafer 200 sometimes become uneven, and the processing of the present invention is effective.

[0194] In addition, in the above-mentioned method, an example of performing the above-mentioned processing sequence in the same processing container of the same processing device (in-situ) is described. The present invention is not limited to the above-mentioned method. For example, any step in the above-mentioned processing sequence and any other step may be performed in different processing containers of different processing devices (ex-situ), or any step in the above-mentioned processing sequence and any other step may be performed in different processing containers of the same processing device.

[0195] In addition, in the above-mentioned manner, an example of supplying an oxidant to the wafer 200 to form an oxide film is described. The present invention is not limited to this, and can also be applied to the case where a film of an element alone, a nitride film, an oxynitride film, and a carbonized film are formed on the wafer 200 (concave structure). In these cases, as a reaction gas, at least one of an oxidant, a nitriding agent, a carbonizing agent, and a reducing agent can be used. The oxidant can use the gas of the present invention. As a nitriding agent, at least one of NH3 gas, N2H4 gas, N2H2 gas, etc. can be used. As a carbonizing agent, at least one of a gas containing alkanes, a gas containing alcohols such as methanol, ethanol, and propanol, etc. can be used. In addition, as a reducing agent, at least one of H2 gas, NH3 gas, monosilane (SiH4) gas, disilane (Si2H6) gas, trisilane (Si3H8) gas, monoborane (BH4) gas, diborane (B2H6) gas, triborane (B3H8) gas, etc. can be used.

[0196] Also when these substrate processing apparatuses are used, each process can be performed in the same process steps and process conditions as those in the above-mentioned embodiment, and the same effects as those in the above-mentioned embodiment can be obtained.

[0197] The above-mentioned methods can be used in combination as appropriate. The processing steps and processing conditions in this case can be, for example, the same as the processing steps and processing conditions in the above-mentioned methods.

[0198] Example

[0199] (Example)

[0200] As an example, the above substrate processing apparatus is used to Figure 5 The processing sequence shown is an example of forming a hafnium oxide film (HfO film) on a pattern wafer having a concave structure formed on the surface. As a modifier, a raw material, an oxidant, and an inert gas, a predetermined substance is selected from the substance group shown in the above method. The processing conditions when performing each step are the predetermined conditions within the range of the processing conditions in each step shown in the above method. Figure 8 (a) shows a schematic structure of partial film formation (here, Hf layer) near the concave structure, ligand and adsorption of inhibitor (here, NH- group from NH3). This structure shows adsorption after the step of supplying raw material gas and the step of supplying NH3 after the supply of raw material gas in the method of forming HfO film. Figure 8 In (a), the mark "AMN" represents the NH- group from NH3, the mark "RGD" represents the ligand, and the mark "MTL" represents the first element of the raw material (for example, hafnium atom). In the NH3 supply of the subsequent pulse of the split process, NH3 can be supplied to the part where the NH- group has not been adsorbed (for example, the wafer 200 and the first layer in the film formation), and the same NH-capping can be formed near the opening of the concave structure of the wafer 200.

[0201] As a comparative example, the above-mentioned substrate processing apparatus was used. Figure 5 In the processing sequence shown, step A is set as a processing sequence that is not implemented, and a HfO film is formed on a pattern wafer having a concave structure formed on the surface. As raw materials, oxidants, and inert gases, the same substances as those used in the embodiment are selected. The processing conditions when performing each step are set to the specified conditions within the range of the processing conditions in each step of the embodiment. Figure 8 (b) shows a schematic structure of partial film formation (here, Hf layer) and ligand adsorption near the concave structure. This structure shows adsorption after the step of supplying raw material gas in the method of forming the HfO film. Figure 8 The reference numerals in (b) are the same as Figure 8 The figure numbers of (a) are the same. Figure 8 In (b), no NH-groups from NH3 are present. The ligand is adsorbed near the opening of the concave structure.

[0202] Then, for the examples and comparative examples, the thickness of the HfO film formed in the concave structure was measured. The film thickness was measured at two locations, the periphery of the opening (TOP) and the periphery of the bottom (BTM) in the concave structure. Then, the cycle rate at each measurement location, that is, the thickness of the HfO film formed per cycle ( / cycle). In addition, as an index showing whether the step coverage is good or not, a value (Step Coverage) obtained by (cycle rate at BTM / cycle rate at TOP)×100(%) was calculated.

[0203] The results are as follows Fig. 9 shown. Fig. 9 The left vertical axis represents the cycle rate ( / cycle), and the right vertical axis represents step coverage (%). Fig. 9 The horizontal axis represents the comparative example and the embodiment in turn. The "◆" mark in the figure represents the cycle rate at TOP, the "■" mark represents the cycle rate at BTM, and the bar graph represents the step coverage (%).

[0204] like Fig. 9 As shown in the figure, it can be seen that the cycle rate at the TOP portion in the embodiment is appropriately suppressed compared with the comparative example, resulting in an improvement in the step coverage (%). This is considered to be because, as described in the above method, the adsorption layer is formed by performing step A at a predetermined time, and thus the adsorption layer hinders the adsorption of the ligand and suppresses the entry of by-products into the HfO film.

[0205] The above-mentioned aspects and modifications can be used in combination as appropriate. The processing steps and processing conditions in this case can be, for example, the same as those of the above-mentioned aspects and modifications.

Claims

1. A substrate processing method, comprising the steps of performing (a), (b) and (c) in sequence a predetermined number of times to form a film containing an element contained in a raw material gas and an element contained in a reaction gas on a substrate, wherein: (a) a step of supplying a first gas containing NH − to the substrate; (b) a step of supplying the raw material gas to the substrate; (c) is a step of supplying the reaction gas to the substrate.

2. The substrate processing method according to claim 1, wherein: The raw material gas is a gas containing amino groups.

3. The substrate processing method according to claim 2, wherein: The feed gas also contains an organic ligand.

4. The substrate processing method according to claim 1, wherein: The film does not contain the element contained in the first gas.

5. The substrate processing method according to claim 1, wherein: The first gas does not contain an organic ligand.

6. The substrate processing method according to claim 1 or 5, wherein: In (a), a second gas containing an organic ligand and NH - is further supplied.

7. The substrate processing method according to claim 6, wherein: In (a), the first gas is supplied after the second gas is supplied.

8. The substrate processing method according to claim 6, wherein: In (a), the second gas is supplied after the first gas is supplied.

9. The substrate processing method according to claim 6, wherein: In (a), there is a period in which the period in which the first gas is supplied overlaps with the period in which the second gas is supplied.

10. The substrate processing method according to claim 1, wherein: In (a), the gas containing NH − is supplied multiple times.

11. The substrate processing method according to claim 1, wherein: In (a), the first gas is supplied in a state where it is not decomposed.

12. The substrate processing method according to claim 1, wherein: (a) is carried out at a higher pressure than that in (b).

13. The substrate processing method according to claim 1, wherein: The supply amount of the first gas is smaller than the supply amount of the raw material gas.

14. The substrate processing method according to claim 1, wherein: A supply amount of the first gas is smaller than a supply amount of the reaction gas.

15. A method for manufacturing a semiconductor device, comprising the steps of performing (a), (b) and (c) in sequence a predetermined number of times to form a film containing an element contained in a raw material gas and an element contained in a reaction gas on a substrate, wherein: (a) a step of supplying a first gas containing NH − to the substrate; (b) a step of supplying the raw material gas to the substrate; (c) is a step of supplying the reaction gas to the substrate.

16. A computer-readable recording medium recording a program for causing a substrate processing apparatus to execute, by a computer, the steps of performing (a), (b) and (c) in sequence a predetermined number of times to form a film containing an element contained in a raw material gas and an element contained in a reaction gas on a substrate, wherein: (a) a step of supplying a first gas containing NH − to the substrate; (b) a step of supplying the raw material gas to the substrate; (c) is a step of supplying the reaction gas to the substrate.

17. A substrate processing apparatus comprising: a first gas supply system for supplying a first gas containing NH − to the substrate; a second gas supply system for supplying a raw material gas to the substrate; a third gas supply system for supplying a reaction gas to the substrate; and The control unit is configured to control the first gas supply system, the second gas supply system, and the third gas supply system in such a manner that (a), (b), and (c) are performed sequentially a predetermined number of times to form a film containing the element contained in the raw material gas and the element contained in the reaction gas on the substrate, wherein: (a) is a process of supplying the first gas containing NH − to the substrate; (b) is a process of supplying the raw material gas to the substrate; and (c) is a process of supplying the reaction gas to the substrate.

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