Substrate processing method, method for producing semiconductor device, program, and substrate processing device

Abstract

This substrate processing method comprises: (a) a step in which a first material, which includes a first element as a film-forming element, is supplied to a substate; (b) a step in which a second material, which includes a second element as a film-forming element, is supplied to the substate; (c) a step in which a third material, which includes a third element as a film-additive element, is supplied to the substrate; and (d) a step in which the steps (a), (b), and (c) are conducted a predetermined number of times to form a film comprising the first element, the second element, and the third element. The difference in electronegativity between the third element and the second element is greater than the difference in electronegativity between the first element and the second element.

Description

SUBSTRATE PROCESSING METHOD, SEMICONDUCTOR DEVICE MANUFACTURING METHOD, PROGRAM, AND SUBSTRATE PROCESSING METHOD

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

[0002] 2. Description of the Related Art One step in the manufacturing process of a semiconductor device is a substrate processing step in which a source gas and a reactive gas are supplied to a substrate to form a film on the substrate (see, for example, Patent Document 1).

[0003] Patent Document 1: Japanese Patent Application Laid-Open No. 2014-135475

[0004] The present disclosure provides a technique that can improve the properties of a film formed on a substrate.

[0005] According to one aspect of the present disclosure, there is provided a technique including: (a) supplying a first material containing a first element constituting a film to a substrate; (b) supplying a second material containing a second element constituting the film to the substrate; (c) supplying a third material containing a third element to be added to the film to the substrate; and (d) performing (a), (b), and (c) a predetermined number of times to form a film containing the first element, the second element, and the third element, wherein the difference between the electronegativity of the third element and the electronegativity of the second element is greater than the difference between the electronegativity of the first element and the electronegativity of the second element.

[0006] According to the present disclosure, it is possible to provide a technique that can improve the properties of a film formed on a substrate.

[0007] Fig. 1 is a longitudinal cross-sectional view showing an outline of a vertical processing furnace of a substrate processing apparatus according to one embodiment. Fig. 2 is a schematic transverse cross-sectional view taken along line A-A in Fig. 1. Fig. 3 is a schematic configuration diagram of a controller of a substrate processing apparatus according to one embodiment, showing a control system of the controller in a block diagram. Fig. 4 is a diagram showing an example of a substrate processing process according to one embodiment.

[0008] Hereinafter, one embodiment of the present disclosure will be described mainly with reference to FIGS. 1 to 4. Note that all drawings used in the following description are schematic. The dimensional relationships and ratios of elements shown in the drawings do not necessarily match those in reality. The dimensional relationships and ratios of elements between multiple drawings also do not necessarily match.

[0009] (1) Configuration of the Substrate Processing Apparatus The substrate processing apparatus 10 includes a processing furnace 202 provided with a heater 207 as a heating means (heating mechanism, heating system). The heater 207 has a cylindrical shape and is installed vertically by being supported by a heater base (not shown) as a holding plate.

[0010] An outer tube 203 constituting a reaction tube (i.e., a reaction vessel and a processing vessel) is disposed concentrically inside the heater 207. The outer tube 203 is made of a heat-resistant material such as quartz or silicon carbide (SiC). The outer tube 203 is formed in a cylindrical shape with a closed upper end and an open lower end. A manifold 209 (hereinafter, MF 209) is disposed concentrically below the outer tube 203. The MF 209 is made of a metal such as stainless steel. The MF 209 is formed in a cylindrical shape with open upper and lower ends. An O-ring 220a is provided as a sealing member between the upper end of the MF 209 and the outer tube 203. The MF 209 is supported on a heater base, so that the outer tube 203 is installed vertically.

[0011] An inner tube 204 constituting a reaction vessel is disposed inside the outer tube 203. The inner tube 204 is made of a heat-resistant material such as quartz or SiC. The inner tube 204 is formed in a cylindrical shape with a closed upper end and an open lower end. The outer tube 203, the inner tube 204, and the MF 209 mainly constitute a processing vessel (i.e., a reaction vessel). A processing chamber 201 is formed in the cylindrical hollow portion of the processing vessel (i.e., inside the inner tube 204).

[0012] The processing chamber 201 is configured to accommodate wafers 200 as substrates arranged in multiple stages in the vertical direction in a horizontal position on boats 217 as supports.

[0013] Nozzles 410, 420, and 430 are provided in the processing chamber 201 so as to penetrate the sidewall of the MF 209 and the inner pipe 204. Gas supply pipes 310, 320, and 330 are connected to the nozzles 410, 420, and 430, respectively. However, the processing furnace 202 of this embodiment is not limited to the above-mentioned configuration.

[0014] Mass flow controllers (MFCs) 312, 322, and 332, which are flow rate controllers (flow rate control parts), are provided in the gas supply pipes 310, 320, and 330, respectively, from the upstream side. Valves 314, 324, and 334, which are on-off valves, are provided in the gas supply pipes 310, 320, and 330, respectively. Gas supply pipes 510, 520, and 530, which supply inert gas, are connected to the downstream sides of the valves 314, 324, and 334 of the gas supply pipes 310, 320, and 330, respectively. MFCs 512, 522, and 532, which are flow rate controllers (flow rate control parts), and valves 514, 524, and 534, which are on-off valves, are provided in the gas supply pipes 510, 520, and 530, respectively, from the upstream side.

[0015] Nozzles 410, 420, and 430 are connected to the tips of the gas supply pipes 310, 320, and 330, respectively. The nozzles 410, 420, and 430 are configured as L-shaped nozzles. The horizontal portions of the nozzles 410, 420, and 430 are arranged to penetrate the side wall of the MF 209 and the inner pipe 204. The vertical portions of the nozzles 410, 420, and 430 are arranged inside the preliminary chamber 201a. The preliminary chamber 201a has a channel shape (groove shape) that protrudes radially outward from the inner pipe 204 and extends vertically. The vertical portions of the nozzles 410, 420, and 430 are arranged in the preliminary chamber 201a along the inner wall of the inner pipe 204, facing upward (upward in the arrangement direction of the wafers 200).

[0016] The nozzles 410, 420, and 430 are provided to extend from a lower region of the processing chamber 201 to an upper region of the processing chamber 201. A plurality of gas supply holes 410a, 420a, and 430a are provided in the nozzles 410, 420, and 430 at positions facing the wafer 200. Thus, processing gas is supplied to the wafer 200 from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430, respectively. The gas supply holes 410a, 420a, and 430a are provided in plurality from the lower portion to the upper portion of the inner tube 204. The gas supply holes 410a, 420a, and 430a each have the same opening area. Furthermore, the gas supply holes 410a, 420a, and 430a are arranged at the same pitch. However, the gas supply holes 410a, 420a, and 430a are not limited to the above-described configuration. For example, the opening areas of the gas supply holes 410 a, 420 a, and 430 a may be gradually increased from the bottom to the top of the inner tube 204. This makes it possible to more uniform the flow rates of gas supplied to the wafers 200 from the gas supply holes 410 a, 420 a, and 430 a.

[0017] The gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 are provided in plurality from the bottom to the top of the boat 217. Therefore, the process gas supplied into the process chamber 201 from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 is supplied to the entire area of ​​the wafers 200 accommodated from the bottom to the top of the boat 217. The nozzles 410, 420, 430 may be provided so as to extend from the bottom region to the top region of the process chamber 201, but are preferably provided so as to extend to near the ceiling of the boat 217.

[0018] A first material is supplied from the gas supply pipe 310 into the process chamber 201 via the MFC 312, the valve 314, and the nozzle 410. In this disclosure, the first material is also referred to as a raw material, a raw material agent, or a source. When the first material is in a gaseous state, the first material in a gaseous state is also referred to as a first gas, a raw material gas, a source gas, or the like.

[0019] The second material is supplied from the gas supply pipe 320 into the process chamber 201 via the MFC 322, the valve 324, and the nozzle 420. In this disclosure, the second material is also referred to as a reactant, a reactant, or a reactant. When the second material is in a gaseous state, the gaseous second material is also referred to as a second gas, a reaction gas, a reactant gas, or the like.

[0020] The third material is supplied from the gas supply pipe 330 into the process chamber 201 via the MFC 332, the valve 334, and the nozzle 430. In this disclosure, the third material is also referred to as a dopant, a doping agent, an additive, etc. When the third material is in a gaseous state, it is also referred to as a third gas, a doping gas, an additive gas, etc.

[0021] In the present disclosure, the term "agent" as used herein includes at least one of a gaseous substance and a liquid substance. Liquid substances include mist-like substances. That is, the conditioning agent may include a gaseous substance, a liquid substance such as a mist-like substance, or both.

[0022] From the gas supply pipes 510, 520, and 530, an inert gas such as nitrogen (N ２ ) gases are supplied into the processing chamber 201 via MFCs 512, 522, and 532, valves 514, 524, and 534, and nozzles 410, 420, and 430, respectively. Hereinafter, N ２ An example of using gas will be described. In the present disclosure, N is used as the inert gas. ２ In addition to the gas, for example, a rare gas such as Ar gas, He gas, Ne gas, or Xe gas may be used.

[0023] When a first material is flowed from the gas supply pipe 310, a first material supply system (first gas supply system) is mainly composed of the gas supply pipe 310, the MFC 312, and the valve 314, but the nozzle 410 may be considered to be included in the first material supply system. When a second material is flowed from the gas supply pipe 320, a second material supply system (second gas supply system) is mainly composed of the gas supply pipe 320, the MFC 322, and the valve 324, but the nozzle 420 may be considered to be included in the second material supply system. When a third material is flowed from the gas supply pipe 330, a third material supply system (third gas supply system) is mainly composed of the gas supply pipe 330, the MFC 332, and the valve 334, but the nozzle 430 may be considered to be included in the adjuster supply system. The first material supply system, the second material supply system, and the third material supply system form a process gas supply system. The process gas supply system may include the nozzles 410, 420, and 430. The gas supply pipes 510, 520, and 530, the MFCs 512, 522, and 532, and the valves 514, 524, and 534 mainly constitute an inert gas supply system.

[0024] The gas supply pipe 310 may be provided with a reservoir 701 for storing the first material, and a valve 702 at the downstream side of the reservoir 701 (i.e., the processing chamber 201).

[0025] In this embodiment, the inner wall of the inner tube 204 and the ends of the multiple wafers 200 define a vertically elongated annular space. Gas is delivered into the inner tube 204 via nozzles 410, 420, and 430 disposed in a pre-chamber 201a within the vertically elongated annular space. The gas is then ejected into the inner tube 204 from multiple gas supply holes 410a, 420a, and 430a provided in the nozzles 410, 420, and 430 at positions facing the wafers 200. More specifically, gas is ejected in a direction parallel to the surface of the wafers 200 from the gas supply hole 410a of the nozzle 410, the gas supply hole 420a of the nozzle 420, and the gas supply hole 430a of the nozzle 430.

[0026] The exhaust hole (exhaust port) 204a is a through-hole formed in the sidewall of the inner tube 204 at a position facing the nozzles 410, 420, and 430. The exhaust hole 204a is, for example, a slit-shaped through-hole that is elongated in the vertical direction. Gas is supplied into the processing chamber 201 from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430 and flows over the surface of the wafer 200. The gas flows through the exhaust hole 204a into the gap (i.e., into the exhaust path 206) formed between the inner tube 204 and the outer tube 203. The gas that flows into the exhaust path 206 then flows into the exhaust pipe 231 and is discharged to the outside of the processing furnace 202.

[0027] The exhaust hole 204a is provided at a position facing the plurality of wafers 200. The gas supplied from the gas supply holes 410a, 420a, and 430a to the vicinity of the wafers 200 in the processing chamber 201 flows horizontally and then flows into the exhaust path 206 through the exhaust hole 204a. The exhaust hole 204a is not limited to being configured as a slit-shaped through-hole, and may be configured as a plurality of holes.

[0028] An exhaust pipe 231 for exhausting the atmosphere in the process chamber 201 is connected to an exhaust port 231a provided in the MF 209. The exhaust pipe 231 is connected to, in order from upstream, a pressure sensor 245 serving as a pressure detector (pressure detection unit) for detecting the pressure in the process chamber 201, an APC (Auto Pressure Controller) valve 243, and a vacuum pump 246 serving as a vacuum exhaust device. The APC valve 243 can evacuate and stop the vacuum exhaust of the process chamber 201 by opening and closing the valve while the vacuum pump 246 is operating. Furthermore, the APC valve 243 can adjust the pressure in the process chamber 201 by adjusting the valve opening while the vacuum pump 246 is operating. An exhaust system is mainly composed of the exhaust hole 204a, the exhaust path 206, the exhaust pipe 231, the APC valve 243, and the pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

[0029] A seal cap 219 (hereinafter also referred to as SC219) is provided below the MF209 as a furnace port cover capable of airtightly closing the lower end opening of the MF209. The SC219 is configured to abut against the lower end of the MF209 from below in the vertical direction. The SC219 is made of a metal such as SUS and is formed in a disk shape. An O-ring 220b is provided on the upper surface of the SC219 as a sealing member that abuts against the lower end of the MF209. A rotation mechanism 267 is installed on the opposite side of the SC219 from the process chamber 201 to rotate a boat 217 that accommodates wafers 200. A rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217 through the SC219. The rotation mechanism 267 is configured to rotate the boat 217 to rotate the wafers 200. The SC 219 is configured to be raised and lowered in the vertical direction by a boat elevator 115 (hereinafter also referred to as BE 115) as a lifting mechanism installed vertically outside the outer tube 203. The BE 115 is configured to be able to load and unload the boat 217 into and out of the processing chamber 201 by lifting and lowering the SC 219. The BE 115 is configured as a transfer device (i.e., a transfer mechanism and a transfer system) that transfers the boat 217 and the wafers 200 accommodated in the boat 217 into and out of the processing chamber 201.

[0030] The boat 217 is configured to hold multiple wafers 200, for example, 25 to 200, arranged horizontally and with their centers aligned and spaced apart in the vertical direction. The boat 217 is made of a heat-resistant material, such as quartz or SiC. Dummy substrates 218 are supported horizontally in multiple stages at the bottom of the boat 217. The dummy substrates 218 are made of a heat-resistant material, such as quartz or SiC. This configuration makes it difficult for heat from the heater 207 to be transmitted to the SC 219. However, this embodiment is not limited to the above-described configuration. For example, a heat insulating cylinder may be provided at the bottom of the boat 217 instead of the dummy substrates 218. The heat insulating cylinder is a cylindrical member made of a heat-resistant material, such as quartz or SiC.

[0031] 2, a temperature sensor 263 serving as a temperature detector is installed inside the inner pipe 204. The substrate processing apparatus 10 is configured to adjust the amount of power supplied to the heater 207 based on temperature information detected by the temperature sensor 263, thereby achieving a desired temperature distribution inside the processing chamber 201. The temperature sensor 263 is configured in an L-shape, similar to the nozzles 410, 420, and 430, and is installed along the inner wall of the inner pipe 204.

[0032] As shown in FIG. 3 , the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are connected to the CPU 121a via an internal bus so as to enable data exchange. An input / output device 122, such as a touch panel, is connected to the controller 121. The substrate processing apparatus may be configured to include one control unit or multiple control units. That is, control for performing the processing sequence described below may be performed using one control unit or multiple control units. The multiple control units may be configured as a control system connected to each other via a wired or wireless communication network, and control for performing the processing sequence described below may be performed by the entire control system. In this specification, when the term "control unit" is used, it may include one control unit, multiple control units, or a control system configured by multiple control units.

[0033] The storage device 121c is configured, for example, with a flash memory or an HDD (Hard Disk Drive). The storage device 121c readably stores a control program for controlling the operation of the substrate processing apparatus, a process recipe describing the procedures and conditions of a semiconductor device manufacturing method (substrate processing method) described later, and other information. The process recipe is a combination of processes (steps) in a semiconductor device manufacturing method (substrate processing method) described later that are executed by the controller 121 to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe and the control program are collectively referred to simply as a program. In this specification, the term "program" may refer to a process recipe alone, a control program alone, or a combination of a process recipe and a control program. The RAM 121b is configured as a memory area for temporarily storing programs, data, and other information read by the CPU 121a.

[0034] The I / O port 121d is connected to the above-mentioned MFCs 312, 322, 332, 512, 522, 532, valves 314, 324, 334, 514, 524, 534, 702, pressure sensor 245, APC valve 243, vacuum pump 246, heater 207, temperature sensor 263, rotation mechanism 267, BE 115, etc.

[0035] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a process recipe or the like from the storage device 121c in response to an input of an operation command from the input / output device 122. The CPU 121a is configured to be able to control a specific operation in accordance with the contents of the read process recipe. The specific operations include flow rate adjustment of various gases by MFCs 312, 322, 332, 512, 522, and 532, opening and closing of valves 314, 324, 334, 514, 524, 534, and 702, gas storage in storage section 701 by valve 702, opening and closing of APC valve 243, pressure adjustment by APC valve 243 based on pressure sensor 245, temperature adjustment of heater 207 based on temperature sensor 263, starting and stopping of vacuum pump 246, rotation and rotation speed adjustment of boat 217 by rotation mechanism 267, raising and lowering of boat 217 by BE 115, and storing wafers 200 in boat 217.

[0036] The controller 121 can be configured by installing the above-mentioned program stored in an external storage device (e.g., a magnetic disk such as a hard disk, an optical disk such as a CD or a DVD, or a semiconductor memory such as a flash memory or a memory card) 123 into a computer. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to as recording media. In this specification, the recording medium may include only the storage device 121c, only the external storage device 123, or both the storage device 121c and the external storage device 123. The program (program product) may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0037] (2) Substrate Processing Step As one step in the manufacturing process of a semiconductor device, an example of a step of forming a silicon nitride (SiN) film, which is used as a charge trap film for 3D NAND, on a wafer 200 will be described with reference to FIG. 4 . The step of forming the SiN film is performed using the processing furnace 202 of the substrate processing apparatus 10 described above. Note that in this embodiment, an example will be described in which the wafer 200 is a substrate (wafer) having recesses such as trenches and holes formed in its surface. In the following description, the operation of each component of the substrate processing apparatus 10 is configured to be controllable by a controller 121.

[0038] The substrate processing process (semiconductor device manufacturing process) according to this embodiment includes: (a) a step of supplying a first material containing a first element constituting the film to the wafer 200; (b) a step of supplying a second material containing a second element constituting the film to the wafer 200; (c) a step of supplying a third material containing a third element, which is an element to be added to the film, to the wafer 200; and (d) a step of performing (a), (b), and (c) a predetermined number of times to form a film containing the first element, the second element, and the third element on the wafer 200. The difference between the electronegativity of the third element and the electronegativity of the second element is larger than the difference between the electronegativity of the first element and the electronegativity of the second element.

[0039] In the present disclosure, the above-described processing sequence includes the following sequences (A) to (G): The same notations as below will be used in the description of other embodiments.

[0040] (A) (first material → second material → third material) × Xa (B) (first material → third material → second material) × Xb (C) (second material → third material → first material) × Xc (D) (third material → second material → first material) × Xd (E) (first material + second material + third material) × Xe (F) (first material + second material → third material) × Xf (G) (second material + third material → first material) × Xg where Xa to Xg are natural numbers (1 or an integer of 2 or more). "→" means that different types of materials are supplied in order, and "+" means that different types of materials are supplied simultaneously. Supplying different types of materials simultaneously means that there is a period during which different types of materials are supplied overlappingly. Note that a process of removing materials present on the wafer 200 (also simply referred to as a purging process) may be performed between →.

[0041] In this specification, the term "wafer" may mean "the wafer itself" or "a laminate of a wafer and a predetermined layer, film, etc. formed on its surface." In this specification, the term "surface of a wafer" may mean "the surface of the wafer itself" or "the surface of a predetermined layer, film, etc. formed on the wafer." In this specification, the phrase "forming a predetermined layer on a wafer" may mean forming a predetermined layer directly on the surface of the wafer itself, or forming a predetermined layer on a layer, etc. formed on the wafer. In this specification, the term "substrate" is synonymous with the term "wafer."

[0042] (Selection of Third Element) The third element is selected. The doping element (i.e., the third element) can be selected based on, for example, the following criteria A) to D): A) Electronegativity B) Atomic size C) Coordination number D) Type of element

[0043] (A: Selection Based on Electronegativity) Here, the selection of the third element based on electronegativity will be described for the case where the film formed on the wafer 200 is the following film: The case where the first element contained in the film is a Group 14 element (e.g., silicon (Si)), and the second element contained in the film is a Group 15 element (e.g., nitrogen (N)) will be described.

[0044] The third element to be added to the film can be selected based on the relationship between the electronegativity of the third element and that of the second element and the relationship between the electronegativity of the first element and that of the second element. For example, the third element is selected so that the difference between the electronegativity of the third element and that of the second element is greater than the difference between the electronegativity of the first element and that of the second element. By selecting the third element based on this relationship, electrons of the third element in the film are attracted to the second element, making it easier for the third element to be positively charged. When the film is made of SiN and the third element is positively charged, electrons of the first element in the film are attracted to the third element, causing the first element to be slightly positively charged. As a result, a level is created around the first element where electrons can be trapped. By utilizing this effect to form a charge trap layer in a semiconductor device, the charge trapping ability of the semiconductor device can be improved.

[0045] Preferably, the third element has a lower electronegativity than the second element. More preferably, the third element has a lower electronegativity than the first element. By selecting the third element based on the electronegativity relationship between the elements, the above-mentioned effects can be further enhanced.

[0046] (B: Selection by atomic size) When selecting a third element based on its atomic size, it is preferable that the atomic size of the third element is approximately the same as that of the first element. In other words, the atomic size of the third element is closer to that of the first element than to that of the second element. The closer the atomic size of the third element is to that of the first element, the lower the atomic packing factor in the film can be. By lowering the atomic packing factor in the film, the space for trapping (capturing) electrons can be increased.

[0047] Preferably, the third element is an element larger than the atomic size of the first element and close to the atomic size of the first element. More preferably, the third element is an element larger than the atomic size of the second element and smaller than the atomic size of an element in the same group as the first element but different from the first element. For example, if the first element is Si, the second element is N, and the third element is an element larger than the atomic size of N and smaller than the atomic size of tin (Sn), which is an element in the same group 14 as Si, the third element can form the same four covalent bonds as Si, and Si can be substituted for the third element. This increases the space for trapping electrons. In other words, the amount of trapped electrons can be increased.

[0048] (C: Selection Based on Coordination Number) A case where the film is made of SiN will be described. The third element is preferably an element capable of tri- or tetra-coordination. Tri-coordination means that the third element has three ligands. Tetra-coordination means that the third element has four ligands. The fact that the third element can be tri-coordinated means that the third element can form three ligands. The fact that the third element can be tetra-coordinated means that the third element can form four ligands. The bond between these ligands is at least one of a covalent bond, a coordinate bond, and an ionic bond. When the third element is an element capable of tri- or tetra-coordination, the space for trapping electrons can be increased. In other words, the amount of trapped electrons can be increased. Preferably, the third element is an element capable of tri-coordination. When a tetra-coordinated element is compared with a tetra-coordinated element, the tetra-coordinated element may be able to increase the space for trapping electrons.

[0049] (D: Selection by Type of Element) A case where the film is made of SiN will be described. Preferably, the third element is a metal element. When the third element is a metal element, the same effect as described above can be obtained. Preferably, the third element is at least one of elements in Periods 3, 4, and 5 of the periodic table. More preferably, the third element is at least one of elements in Periods 3, 4, and 5 of the periodic table. Preferably, the third element is a transition metal element. Preferably, the third element is a non-transition metal element. Non-transition metal elements also meet the selection criteria (A), (B), and (C) described above and can increase the amount of electron traps. Examples of such non-transition metal elements include zinc (Zn), gallium (Ga), aluminum (Al), and indium (In). More preferably, the third element is at least one of Al, Zn, Ga, and In. More preferably, the third element is at least one of Zn, Ga, and In. By using these elements as the third element, it is possible to trap more electrons. In other words, it is possible to increase the amount of trapped electrons.

[0050] A preparation step is performed to supply the third material containing the third element selected according to the above-described selection criteria to the wafer 200 .

[0051] 1, the boat 217 supporting the wafers 200 is lifted by the BE 115 and loaded into the processing chamber 201. The boat 217 supporting the wafers 200 is then housed in the processing vessel. In this state, the SC 219 closes the lower end opening of the outer tube 203 via the O-ring 220.

[0052] (Pressure Regulation and Temperature Regulation) The processing chamber 201 is evacuated by the vacuum pump 246 so that the processing chamber 201 (i.e., the space in which the wafer 200 is present) reaches a desired pressure. At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245. Then, based on the pressure information measured by the pressure sensor 245, the APC valve 243 is feedback-controlled (pressure regulation). The vacuum pump 246 remains in a constantly operating state until the processing of the wafer 200 is completed. The processing chamber 201 is heated by the heater 207 so that the processing chamber 201 reaches a desired temperature. At this time, the amount of power supplied to the heater 207 is feedback-controlled based on temperature information detected by the temperature sensor 263 so that the processing chamber 201 achieves a desired temperature distribution (temperature regulation). The heating of the processing chamber 201 by the heater 207 continues until the processing of the wafer 200 is completed.

[0053] (Film Forming Process) Next, the film forming process is performed. The film forming process includes a first material supplying process, a purging process, a second material supplying process, a purging process, a third material supplying process, a purging process, and a process of determining whether these processes have been performed a predetermined number of times (n times, where n is 1 or an integer equal to or greater than 1). Each of these processes will be described below.

[0054] (First Material Supply Process: First Process) The controller 121 opens the valve 314 to flow the first material into the gas supply pipe 310. The flow rate of the first material is adjusted by the MFC 312, and then the first material is supplied into the processing chamber 201 from the gas supply holes 410a of the nozzle 410. The first material supplied into the processing chamber 201 is exhausted from the exhaust pipe 231. In this way, the first material is supplied to the wafer 200. At this time, the controller 121 opens the valve 514 to supply N 2 into the gas supply pipe 510. ２ An inert gas such as N 2 gas may be flowed through the gas supply pipe 510. ２ The gas is supplied into the processing chamber 201 together with the first material after the flow rate is adjusted by the MFC 512. ２The gas is exhausted from the exhaust pipe 231. At this time, in order to prevent the first material from entering the nozzles 420 and 430, the controller 121 opens the valves 524 and 534 to supply N 2 into the gas supply pipes 520 and 530. ２ Gas may be flowed. ２ The gas is supplied into the processing chamber 201 through the gas supply pipes 320 and 330 and the nozzles 420 and 430 , and then exhausted from the exhaust pipe 231 .

[0055] At this time, the controller 121 adjusts the APC valve 243 to set the pressure inside the processing chamber 201 to, for example, a pressure within a range of 1 to 3990 Pa. The supply flow rate of the raw material controlled by the MFC 312 is, for example, 1 to 2000 sccm, preferably 10 to 1000 sccm. Here, the supply conditions of the first material are set so that the exposure amount of the first material to the wafer 200 is greater than the exposure amount of the third material. Note that the exposure amount of the first material in this disclosure is, for example, the product of the partial pressure of the raw material inside the processing chamber 201 and the supply time of the raw material into the processing chamber 201 (partial pressure x time). The N controlled by the MFCs 512, 522, and 532 ２The supply flow rates of the gases are set, for example, within a range of 0.1 to 5.0 slm. The temperature of the heater 207 is set so that the temperature of the wafer 200 is, for example, within a range of 250 to 800°C, preferably 600 to 700°C. The exposure amount of the first material in the present disclosure may also be the product of the supply flow rate of the first material into the processing chamber 201 and the supply time (supply flow rate x supply time), the product of the total pressure in the processing chamber 201 and the supply time of the first material into the processing chamber 201 (total pressure x supply time), or the product of the partial pressure (total pressure) in the processing chamber 201 and the supply flow rate and supply time of the first material into the processing chamber 201 (partial pressure (total pressure) x supply flow rate x supply time). The supply flow rate of the first material into the processing chamber 201 is affected by the volume of the processing vessel, the pattern of the recesses formed on the wafer 200, and the like. Therefore, it is preferable that the exposure amount of the first material be the product of the partial pressure in the process chamber 201 and the time for which the raw material is supplied into the process chamber 201. Note that in this disclosure, a numerical range such as "1 to 3990 Pa" means that the range includes both the lower limit and the upper limit. Therefore, for example, "1 to 3990 Pa" means "1 Pa or more and 3990 Pa or less." The same applies to other numerical ranges.

[0056] In the present disclosure, the exposure amount of the first material to the wafer 200 can also be rephrased as the adsorption amount of gas molecules adsorbed on the surface of the wafer 200. As described above, this adsorption amount can be adjusted by, for example, the product of the partial pressure of the first material in the processing chamber 201 and the supply time of the first material into the processing chamber 201 (partial pressure x time).

[0057] In the present disclosure, the exposure amount (adsorption amount) of the first material can be made greater than the exposure amount (adsorption amount) of the third material by adjusting at least one of the partial pressure, total pressure, supply flow rate, and supply time related to the exposure amount of the first material to be greater than at least one of the partial pressure, total pressure, supply flow rate, and time related to the exposure amount of the third material.

[0058] The first material may be stored in the storage unit 701 and supplied from the storage unit 701 into the processing chamber 201. When the first material stored in the storage unit 701 is supplied into the processing chamber 201, the supply time of the first material into the processing chamber 201 may be shorter than either the supply time of the second material or the supply time of the third material into the processing chamber 201. In this case, for example, the exposure amounts of the first material, the second material, and the third material are adjusted so that the product of the partial pressure (total pressure) of the first material in the processing chamber 201 and the supply time of the first material into the processing chamber 201 is greater than the product of the partial pressure (total pressure) of the second material (third material) in the processing chamber 201 and the supply time of the second material (third material) into the processing chamber 201. In the first material supply step, the first material may be supplied into the processing chamber 201 not only once but also multiple times. When the first material is supplied into the processing chamber 201 multiple times, the supply of the first material into the processing chamber 201 is stopped between a predetermined supply and the next supply. When the first material is supplied into the processing chamber 201 multiple times, the first material stored in the storage section 701 may be supplied into the processing chamber 201 at least once. For example, when the first material is supplied into the processing chamber 201 two or more times, the first material stored in the storage section 701 is supplied into the processing chamber 201 in the first supply, and the first material is supplied into the processing chamber 201 without storing any raw material in the storage section 701 in the second supply. Note that the supply of the first material into the processing chamber 201 is stopped between the first and second supplies. The processing chamber 201 may be evacuated (reduced pressure) in conjunction with the halt of the supply of the first material into the processing chamber 201, or an inert gas may be supplied into the processing chamber 201 in conjunction with the evacuation. The supply and stop of the first material into the processing chamber 201 is controlled by, for example, opening and closing a valve 702 .

[0059] The first material (raw material) supplied to the wafer 200 includes, for example, a main element constituting the film formed on the wafer 200. The first material includes a first element. Preferably, the first element is a Group 14 element. The main element of the first material may be, for example, Si. For example, a silane-based gas containing Si can be used as the first material. For example, a gas containing Si and a halogen (i.e., a halosilane gas) can be used as the silane-based gas. Examples of halogens include chlorine (Cl), fluorine (F), bromine (Br), and iodine (I). For example, a chlorosilane gas containing Si and Cl can be used as the halosilane gas.

[0060] The raw material is, for example, monochlorosilane (SiH ３ Cl) gas, dichlorosilane (SiH ２ Cl ２ ) gas, trichlorosilane (SiHCl ３ ) gas, tetrachlorosilane (SiCl ４ ) gas, hexachlorodisilane gas (Si ２ Cl ６ , abbreviated as HCDS) gas and octachlorotrisilane (Si ３ Cl ８ As the first material, one or more of these may be used.

[0061] The first material may be, for example, tetrafluorosilane (SiF ４ ) gas, difluorosilane (SiH ２ F ２ ) gas, tetrabromosilane (SiBr ４ ) gas, dibromosilane (SiH ２ Br ２ ) gas, bromosilane gas such as tetraiodosilane (SiI ４ ) gas, diiodosilane (SiH ２ I ２ It is also possible to use an iodosilane gas such as silane fluoride (SiH) gas. As the first material, one or more of these may be used.

[0062] In addition to these, the first material may also be, for example, a gas containing Si and an amino group (i.e., aminosilane gas). The amino group is a monovalent functional group formed by removing hydrogen (H) from ammonia, a primary amine, or a secondary amine, and is represented by —NH ２ , -NHR, and -NR ２ where R represents an alkyl group, and —NR ２ The two R's may be the same or different.

[0063] The first material may be, for example, tetrakis(dimethylamino)silane (Si[N(CH ３ ) ２ ] ４ ) gas, tris(dimethylamino)silane (Si[N(CH ３ ) ２ ] ３ H) gas, bis(diethylamino)silane (Si[N(C ２ H ５ ) ２ ] ２ H ２ ) gas, bis(tert-butylamino)silane (SiH ２ [NH(C ４ H ９ )] ２ ) gas, and (diisopropylamino)silane (SiH ３ [N(C ３ H ７ ) ２ An aminosilane gas such as a silane gas (silane silane, ...

[0064] In this disclosure, an example using HCDS gas as the first material will be described. When HCDS gas is used as the first material, a Si-containing layer containing Cl of a predetermined thickness can be formed as a first layer on the outermost surface of the wafer 200. The Si-containing layer containing Cl can be formed by physical or chemical adsorption of molecules of the first material, physical or chemical adsorption of molecules of a substance (also referred to as a decomposition product) formed by decomposition of at least a portion of the molecules of the first material, or deposition of Si by thermal decomposition of the first material. When HCDS is used as the first material, the decomposition product can be, for example, SiClx, where x is 2, 3, or 4. The Si-containing layer containing Cl may be an adsorption layer (physical or chemical adsorption layer) of molecules of chlorosilane gas or molecules of a substance formed by decomposition of a portion of the chlorosilane gas, or a deposition layer of Si containing Cl. When the above-mentioned chemical adsorption layer or deposition layer is formed on the outermost surface of the wafer 200, Si contained in the chlorosilane gas is adsorbed on the outermost surface of the wafer 200. In the present disclosure, the Si-containing layer containing Cl is also simply referred to as the Si-containing layer.

[0065] (Purge Process (Removal of Residual Gas)) After a predetermined time (for example, 1 to 60 seconds) has elapsed since the start of supply of the first material, the controller 121 closes the valve 314 (or valve 702) of the gas supply pipe 310 to stop the supply of the first material. In other words, the time for supplying the first material to the wafer 200 is set to, for example, a time within a range of 1 to 60 seconds. At this time, the controller 121 leaves the APC valve 243 of the exhaust pipe 231 open and causes the vacuum pump 246 to evacuate the processing chamber 201, thereby removing the unreacted first material remaining in the processing chamber 201 and the first material after contributing to layer formation from the processing chamber 201. In other words, the controller 121 evacuates the atmosphere in the processing chamber 201. At this time, the controller 121 leaves the valves 514, 524, and 534 open and causes the N ２ The supply of gas into the processing chamber 201 may be maintained. ２ The gas acts as a gas for suppressing the intrusion of gas into each of the nozzles 410, 420, and 430, and also acts as a purge gas. ２When the gas is supplied, it is possible to enhance the effect of removing the unreacted first material remaining in the processing chamber 201 and the first material after contributing to layer formation from the processing chamber 201 .

[0066] (Supply of Second Material: Second Step) After removing the residual gas from the processing chamber 201, the controller 121 opens the valve 324 and flows the second material into the gas supply pipe 320. The flow rate of the second material is adjusted by the MFC 322, and then the second material is supplied into the processing chamber 201 from the gas supply holes 420a of the nozzle 420. The second material supplied into the processing chamber 201 is exhausted from the exhaust pipe 231. At this time, the second material is supplied to the wafer 200. At this time, the controller 121 controls the supply of N 2 gas into the gas supply pipes 510, 520, and 530 while keeping the valves 514, 524, and 534 open. ２ The gas supply is maintained. N2 flows through the gas supply pipes 510, 520, and 530. ２ The flow rates of the gases are adjusted by MFCs 512, 522, and 532. N ２ The gas is supplied into the processing chamber 201 together with the second material through the gas supply pipe 320 and the nozzle 420, and then exhausted from the exhaust pipe 231. ２ The gas is supplied into the processing chamber 201 through the gas supply pipe 330 and the nozzle 430, and then exhausted from the exhaust pipe 231. ２ The gas is supplied into the processing chamber 201 via the gas supply pipe 310 and the nozzle 410, and then exhausted from the exhaust pipe 231. This prevents the second material from entering the nozzle 410.

[0067] At this time, the controller 121 adjusts the APC valve 243 to set the pressure inside the processing chamber 201 to, for example, a pressure within a range of 1 to 13,300 Pa (for example, 5,000 Pa). The supply flow rate of the second material controlled by the MFC 322 is set to, for example, a flow rate within a range of 1 to 50 slm, preferably 15 to 40 slm. ２ The supply flow rates of the gases are set within the range of, for example, 0.1 to 5.0 slm.

[0068] The exposure amount (adsorption amount) of the second material to the wafer 200 is preferably an amount at which the molecules of the second material are saturated by adsorption to the wafer 200. In other words, the exposure amount (adsorption amount) of the second material to the wafer 200 is preferably an amount at which the molecules of the second material are saturated by adsorption to the wafer 200.

[0069] The second material includes a second element. Preferably, the second element is the 15th element. For example, a N- and H-containing gas, which is a nitriding gas (nitriding agent), can be used as the second material supplied to the wafer 200. The N- and H-containing gas is both an N-containing gas and an H-containing gas. The N- and H-containing gas preferably has an N-H bond.

[0070] The second material may be, for example, ammonia (NH ３ ) gas, diazene (N ２ H ２ ) gas, hydrazine (N ２ H ４ ) gas, and N ３ H ８ The second material may be one or more of these gases, such as a hydrogen nitride gas.

[0071] In addition to these, the second material may also be, for example, a gas containing N, carbon (C), and H. The N, C, and H-containing gas may be, for example, an amine-based gas or an organic hydrazine-based gas. The N, C, and H-containing gas may be an N-containing gas, a C-containing gas, an H-containing gas, or an N- and C-containing gas.

[0072] The second material may be, for example, monoethylamine (C ２ H ５ NH ２ ) gas, diethylamine ((C ２ H ５ ) ２ NH) gas, and triethylamine ((C ２ H ５ ) ３ N) gas, and monomethylamine (CH ３ NH ２ ) gas, dimethylamine ((CH ３ ) ２NH) gas, and trimethylamine ((CH ３ ) ３ Methylamine-based gases such as N gas, and monomethylhydrazine ((CH ３ ) HN ２ H ２ ) gas, dimethylhydrazine ((CH ３ ) ２ N ２ H ２ ) gas, and trimethylhydrazine ((CH ３ ) ２ N ２ (CH ３ For example, organic hydrazine-based gases such as HCl, ...

[0073] (Purge Process: Removal of Residual Gas) After a predetermined time (e.g., 1 to 1200 seconds) has elapsed since the start of the supply of the second material, the controller 121 closes the valve 324 of the gas supply pipe 320 to stop the supply of the second material. Then, by a process procedure similar to that of the above-described purge process, any unreacted second material or any reaction by-products remaining in the process chamber 201 after contributing to layer formation are removed from the process chamber 201. That is, the controller 121 exhausts the atmosphere in the process chamber 201.

[0074] (Third Material Supply Process: Third Process) The controller 121 opens the valve 334 to flow the third material into the gas supply pipe 330. The flow rate of the third material is adjusted by the MFC 332, and then the third material is supplied into the processing chamber 201 from the gas supply holes 430a of the nozzle 430. The third material supplied into the processing chamber 201 is exhausted from the exhaust pipe 231. At this time, the third material is supplied to the wafer 200. At this time, the controller 121 opens the valve 534 to supply N 2 O 3 into the gas supply pipe 530. ２ An inert gas such as N 2 gas may be flowed through the gas supply pipe 530. ２ The gas is supplied into the processing chamber 201 together with the third material after the flow rate is adjusted by the MFC 532. ２The gas is exhausted from the exhaust pipe 231. At this time, in order to prevent the third material from entering the nozzles 410 and 420, the controller 121 opens the valves 512 and 524 to supply N 2 into the gas supply pipes 510 and 520. ２ Gas may be flowed. ２ Gas is supplied into the processing chamber 201 through gas supply pipes 310 and 320 and nozzles 410 and 420 and is exhausted from an exhaust pipe 231 .

[0075] At this time, the controller 121 adjusts the APC valve 243 to set the pressure inside the processing chamber 201 within a range of, for example, 1 to 3990 Pa (for example, 1000 Pa). The supply flow rate of the third material controlled by the MFC 332 is set within a range of, for example, 0.005 to 3.0 slm. Here, the controller 121 adjusts the pressure inside the processing chamber 201 and the supply flow rate and supply time of the third material into the processing chamber 201 so that the exposure amount of the third material to the wafer 200 becomes a predetermined exposure amount. Note that the exposure amount of the third material in the present disclosure is calculated, for example, by the product of the partial pressure of the third material in the processing chamber 201 and the supply time of the third material into the processing chamber 201 (partial pressure x time). The exposure amount of the third material is less than the exposure amounts of the first material and the second material. The N controlled by the MFCs 512 and 522 ２ The gas supply flow rate is set to, for example, within a range of 0.1 to 5.0 slm, respectively, in order to prevent the third material from entering each of the nozzles 410 and 420. At this time, the temperature of the heater 207 is set to a temperature such that the temperature of the wafer 200 is within a range of, for example, 250 to 800°C, preferably 600 to 700°C.

[0076] The third material may be, for example, aluminum chloride (AlCl ３ ), gallium chloride (GaCl ３ ), indium chloride (InCl ３ ), zinc chloride (ZnCl ２ ), titanium chloride (TiCl ４ ), zirconium chloride (ZrCl ４ ), and hafnium chloride (HfCl ４A gas of a chloride (i.e., a gas of an inorganic material) such as trimethylaluminum (Al(CH ３ ) ３ ), triethylaluminum (Al(C ２ H ５ ) ３ ), trimethylgallium (Ga(CH ３ ) ３ ), triethylgallium (Ga(C ２ H ５ ) ３ ), trimethylindium (Ga(CH ３ ) ３ ), triethylindium (In(C ２ H ５ ) ３ ), dimethylzinc (Zn(CH ３ ) ２ ), diethyl zinc (Zn(C ２ H ５ ) ２ ), trisdimethylamidocyclopentadienyl hafnium (Hf(C ５ H ５ ) (N (CH ３ ) ２ ) ３ ) gas, tris(dimethylamido)cyclopentadienyl zirconium (Zr(C ５ H ５ ) (N (CH ３ ) ２ ) ３ ), and tetrakisdimethylamidotitanium (Ti((CH ３ ) ２ N) ４ Organic gases containing alkyl groups such as methyl methyl acrylate, methyl meth ...

[0077] (Purge Process: Removal of Residual Gas) After a predetermined time (e.g., 1 to 1200 seconds) has elapsed since the start of the supply of the third material, the controller 121 closes the valve 334 of the gas supply pipe 330 to stop the supply of the third material. Then, by a process procedure similar to that of the above-described purge process, any unreacted third material or any reaction by-products remaining in the process chamber 201 after contributing to the formation of a layer are removed from the process chamber 201. That is, the controller 121 exhausts the atmosphere in the process chamber 201.

[0078] (Performed a Predetermined Number of Times) By performing a cycle of sequentially performing the above-described first, second, and third steps a predetermined number of times (n times, where n is an integer of 1 or 2 or more), a film of an element contained in the first material having a predetermined thickness is formed on the wafer 200. For example, a SiN film can be formed on the wafer 200. It is preferable to repeat the above-described cycle multiple times.

[0079] (Purge and atmospheric pressure return) The controller 121 supplies N ２ The gas is supplied into the processing chamber 201. ２ The gas is exhausted from the exhaust pipe 231. ２ The gas acts as a purge gas. As a result, the inside of the processing chamber 201 is purged with the inert gas, and materials (gases) and reaction by-products remaining in the processing chamber 201 are removed from the inside of the processing chamber 201. Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas, and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure).

[0080] (Wafer Unloading) Thereafter, the SC 219 is lowered by the BE 115 to open the lower end of the outer tube 203. Then, the processed wafers 200 supported by the boat 217 are unloaded from the lower end of the outer tube 203 to the outside of the outer tube 203. Thereafter, the processed wafers 200 are removed from the boat 217.

[0081] (3) Effects of this Embodiment According to this embodiment, one or more of the following effects can be obtained.

[0082] (a) The charge trapping performance of the film formed on the wafer 200 can be improved. (b) The difference between the electronegativity of the third element and the electronegativity of the second element is greater than the difference between the electronegativity of the first element and the electronegativity of the second element. By using a third material containing a third element that satisfies this condition, electrons of the third element in the film are attracted to the second element, making it easier for the third element to carry a positive charge. When the film is made of SiN and the third element carries a positive charge, electrons of the first element in the film are attracted to the third element, causing the first element to carry a slight positive charge. As a result, a level is created around the first element where electrons can be trapped. By utilizing this effect to form a charge trap layer in a semiconductor device, the charge trapping ability of the semiconductor device can be improved. (c) The third element is an element with a lower electronegativity than the second element, thereby further enhancing the effect of (b). (d) The atomic size of the third element is closer to the atomic size of the first element than the atomic size of the second element, thereby reducing the atomic packing factor in the film. Reducing the atomic packing factor in the film increases the space for trapping (capturing) electrons. (e) Preferably, the third element is an element larger than the atomic size of the first element and closer to the atomic size of the first element. More preferably, the third element is an element larger than the atomic size of the second element and smaller than the atomic size of an element in the same group as the first element but different from the first element, thereby increasing the space for trapping electrons. In other words, the amount of trapped electrons can be increased. (f) When the film is made of SiN, the third element is an element that can have three or four coordinations, thereby increasing the space for trapping electrons in SiN. In other words, the amount of trapped electrons can be increased. (g) When the film is made of SiN, preferably, the third element is a metal element. When the third element is a metal element, the same effect as described above can be obtained. More preferably, the metal element is at least one of zinc (Zn), gallium (Ga), aluminum (Al), and indium (In). Even more preferably, the third element is at least one of Zn, Ga, and In.More preferably, In is used. In the case of In, a three-coordinate bond is formed, and the number of trapped electrons can be increased by the mechanism in which electrons enter orbitals that are vacant. When comparing Zn, Ga, Al, and In, the trap depths are in the relationship Zn<Ga<Al<In, with In having the deepest trap depth. Increasing the trap depth can improve electron retention performance. Furthermore, compared with other metal elements (e.g., Hf and Ti), these elements can make it difficult for shallow trap levels to be formed among the levels at which electrons are retained. Here, the shallow trap level is a level close to the conduction band. Even if electrons can be retained at the shallow trap level, the retained electrons may be released due to some influence, which can cause deterioration in device performance. On the other hand, elements such as Zn, Ga, Al, and In make it difficult for shallow trap levels to be formed. Furthermore, for Al and In, the levels that can trap electrons near these elements are formed at levels deeper than the trap levels of the SiN material itself. Therefore, forming a film using these elements can improve the electron retention performance of the device. Note that the deep levels refer to levels that are relatively closer to the valence band than the trap levels of the SiN material itself.

[0083] Other Aspects of the Present Disclosure The above describes specific aspects of the present disclosure. However, the present disclosure is not limited to the above aspects and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0084] For example, although the above embodiment has been described using a gas containing Si as the first material, the present disclosure is not limited thereto, and may be applied to a process using a gas containing at least one element selected from the group 13, 14, 4, 6, and 8 elements as the first material.

[0085] In the above embodiment, a case where a gas containing nitrogen element is used as the second material has been described as an example, but the present disclosure is not limited to this. For example, an oxide film may be formed on the wafer 200 using a gas containing oxygen element as the second material. Examples of the gas containing oxygen include oxygen (O ２ ) gas, water (H ２ O), hydrogen peroxide (H ２ O ２ ) gas, nitrous oxide (dinitrogen oxide) (N ２ O) gas, nitric oxide (NO) gas, and ozone (O ３ ) gas, etc. As the second material, one or more of these gases may be activated or excited and used.

[0086] A gas containing hydrogen element may be used as the second material to form a film containing the element as a main component on the wafer 200. The gas containing hydrogen element may be, for example, hydrogen (H ２ The reactants include gases composed of hydrogen elements such as silane-based gases, borane-based gases, phosphane-based gases, and germane-based gases, and mononuclear parent hydride gases such as silane-based gases, borane-based gases, phosphane-based gases, and germane-based gases. Activated or excited gases of at least one of these gases may also be used as the reactant. Incidentally, the silane-based gases include monosilane (SiH ４ ) gas, disilane (Si ２ H ６ ) gas, and trisilane (Si ３ H ８ ) gases. Borane-based gases include monoborane (BH ３ ) gas, and diborane (B ２ H ６ ) gases. Phosphine gases include phosphine (PH ３ ) gas, and diphosphine (P ２ H ６ ) gases. Germane-based gases include monogermane (GeH ４ ) gas, digermane (Ge ２ H ６ ) gas, and trigermane (Ge ３ H ８ ) Gas, etc.

[0087] In the above embodiment, an example of film formation using a substrate processing apparatus that is a batch-type vertical apparatus that processes multiple substrates at a time has been described. However, the present disclosure is not limited to this and can also be suitably applied to film formation using a single-wafer substrate processing apparatus that processes at least one substrate at a time. In the above aspect, an example of film formation using a substrate processing apparatus having a hot-wall processing furnace has been described. The present disclosure is not limited to this and can also be suitably applied to film formation using a substrate processing apparatus having a cold-wall processing furnace. Even when using these substrate processing apparatuses, film formation can be performed using the same processing sequence and processing conditions as in the above embodiment.

[0088] In the above-described embodiment, the processing sequence is performed in the same processing chamber of the same processing apparatus (in-situ). The present disclosure is not limited to the above-described embodiment, and for example, one step and another step of the processing sequence may be performed in different processing chambers of different processing apparatuses (ex-situ), or may be performed in different processing chambers of the same processing apparatus.

[0089] It is preferable that process recipes (i.e., programs describing processing procedures and processing conditions) used to form these various thin films are individually prepared (i.e., multiple process recipes are prepared) depending on the content of substrate processing (e.g., the type, composition ratio, film quality, film thickness, processing procedure, or processing conditions of the thin film to be formed). Then, when starting substrate processing, it is preferable to appropriately select an appropriate process recipe from the multiple process recipes depending on the content of substrate processing. Specifically, it is preferable that multiple process recipes individually prepared depending on the content of substrate processing are pre-stored (installed) in the storage device 121c of the substrate processing apparatus via an electric communication line or a recording medium (e.g., an external storage device 123) on which the process recipes are recorded. Then, when starting substrate processing, it is preferable that the CPU 121a of the substrate processing apparatus appropriately selects an appropriate process recipe from the multiple process recipes stored in the storage device 121c depending on the content of substrate processing. This configuration enables a single substrate processing apparatus to versatility-wise form thin films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility. Since the operational burden on the operator (for example, the burden of inputting processing procedures, processing conditions, etc.) can be reduced, it becomes possible to quickly start substrate processing while avoiding operational errors by the operator.

[0090] The present disclosure can also be realized, for example, by changing the process recipe of an existing substrate processing apparatus. When changing the process recipe, the process recipe according to the present disclosure can be installed in the existing substrate processing apparatus via an electric communication line or a recording medium on which the process recipe is recorded, or the process recipe itself can be changed to the process recipe according to the present disclosure by operating an input / output device of the existing substrate processing apparatus.

[0091] The above-described embodiments and modifications may be used in combination as appropriate, and the processing procedures and processing conditions in such a case may be the same as those of the above-described embodiments and modifications.

[0092] Although the embodiments of the present disclosure have been specifically described above, the present disclosure is not limited to the above-described embodiments and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0093] The disclosure of Japanese Patent Application No. 2024-052683, filed on March 28, 2024, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A substrate processing method comprising: (a) a step of supplying a first material to a substrate, the first material including a first element that constitutes a film; (b) a step of supplying a second material to the substrate, the second material including a second element that constitutes the film; (c) a step of supplying a third material to the substrate, the third material including a third element that is an element to be added to the film; and (d) a step of performing (a), (b), and (c) a predetermined number of times to form a film including the first element, the second element, and the third element, wherein the difference between the electronegativity of the third element and the electronegativity of the second element is greater than the difference between the electronegativity of the first element and the electronegativity of the second element.

2. The substrate processing method according to claim 1, wherein the third element is an element having a lower electronegativity than the second element.

3. The substrate processing method according to claim 1, wherein the third element is an element having a lower electronegativity than the first element.

4. The substrate processing method according to claim 1, wherein the atomic size of the third element is approximately the same as the atomic size of the first element.

5. The substrate processing method according to claim 1, wherein the atomic size of the third element is closer to the atomic size of the first element than to the atomic size of the second element.

6. The substrate processing method according to claim 1, wherein the third element is an element having an atomic size larger than that of the first element and close to that of the first element.

7. The substrate processing method according to claim 1, wherein the third element is an element having an atomic size larger than that of the second element, and smaller than that of an element in the same group as the first element but different from the first element.

8. The substrate processing method according to claim 1, wherein the third element is an element capable of having three or four coordination atoms.

9. The substrate processing method according to any one of claims 1 to 8, wherein the third element is a metal element.

10. The substrate processing method according to any one of claims 1 to 8, wherein the third element is a transition metal element.

11. The substrate processing method according to any one of claims 1 to 8, wherein the third element is a non-transition metal element.

12. The substrate processing method according to any one of claims 1 to 8, wherein the third element is at least one of elements in the third, fourth, and fifth periods of the periodic table.

13. The substrate processing method according to any one of claims 1 to 8, wherein the third element is at least one of elements in the third and fourth periods of the periodic table.

14. The substrate processing method according to any one of claims 1 to 8, wherein the third element is at least one of Al, Zn, Ga, and In.

15. The substrate processing method according to any one of claims 1 to 8, wherein the third element is at least one of Zn, Ga, and In.

16. The substrate processing method according to claim 1, wherein the first element is a Group 14 element.

17. The substrate processing method according to claim 1, wherein the second element is a Group 15 element.

18. A method for manufacturing a semiconductor device, comprising: (a) a step of supplying a first material containing a first element that constitutes a film to a substrate; (b) a step of supplying a second material containing a second element that constitutes the film to the substrate; (c) a step of supplying a third material containing a third element to be added to the film to the substrate; and (d) a step of performing (a), (b), and (c) a predetermined number of times to form a film that contains the first element, the second element, and the third element, wherein the difference between the electronegativity of the third element and the electronegativity of the second element is greater than the difference between the electronegativity of the first element and the electronegativity of the second element.

19. A program for causing a computer to execute the following steps (a), (b), (c), and (d) in a substrate processing apparatus: (a) a procedure for supplying a first material containing a first element constituting a film to a substrate; (b) a procedure for supplying a second material containing a second element constituting the film to the substrate; (c) a procedure for supplying a third material containing a third element to be added to the film to the substrate, wherein the difference between the electronegativity of the third element and the electronegativity of the second element is greater than the difference between the electronegativity of the first element and the electronegativity of the second element; and (d) a procedure for performing steps (a), (b), and (c) a predetermined number of times to form a film containing the first element, the second element, and the third element.

20. A substrate processing apparatus comprising: a first supply unit that supplies a first material containing a first element that constitutes a film to a substrate; a second supply unit that supplies a second material containing a second element that constitutes the film to the substrate; a third supply unit that supplies a third material containing a third element that is an element to be added to the film; and a control unit configured to be able to control the first supply unit, the second supply unit, and the third supply unit to perform a specific process, wherein the difference between the electronegativity of the third element and the electronegativity of the second element is greater than the difference between the electronegativity of the first element and the electronegativity of the second element, and the specific process comprises: (a) a process of supplying the first material to the substrate; (b) a process of supplying the second material to the substrate; (c) a process of supplying the third material to the substrate; and (d) a process of performing (a), (b), and (c) a predetermined number of times to form a film containing the first element, the second element, and the third element.

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