Substrate processing method, method for manufacturing semiconductor device, program, and substrate processing apparatus

Abstract

The substrate processing method of the present disclosure includes the following steps: (a) a step of supplying a first material to a substrate, wherein the first material contains a first element constituting a film; (b) a step of supplying a second material to the substrate, wherein the second material contains a second element constituting the film; (c) a step of supplying a third material to the substrate, wherein the third material contains a third element added to the film; and (d) a step of performing the 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. 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.

Description

Technical Field

[0001] This disclosure relates to substrate processing methods, semiconductor device manufacturing methods and procedures, and substrate processing apparatus. Background Technology

[0002] As a step in the manufacturing process of a semiconductor device, sometimes a substrate processing step is performed, in which raw material gas and reaction gas are supplied to the substrate to form a film on the substrate (see, for example, Patent Document 1).

[0003] Patent Document 1: Japanese Patent Application Publication No. 2014-135475 Summary of the Invention

[0004] The problem that the invention aims to solve

[0005] This disclosure provides a technique that can improve the properties of films formed on a substrate.

[0006] Methods for solving problems

[0007] According to one aspect of this disclosure, a technique is provided comprising the following steps: (a) supplying a first material to a substrate, wherein the first material comprises a first element constituting a film; (b) supplying a second material to the substrate, wherein the second material comprises a second element constituting a film; (c) supplying a third material to the substrate, wherein the third material comprises an element added to the film, namely a third element; and (d) performing steps (a), (b), and (c) 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.

[0008] Invention Effects

[0009] According to this disclosure, a technique can be provided to improve the properties of a film formed on a substrate. Attached Figure Description

[0010] Figure 1 This is a schematic longitudinal sectional view of a vertical processing furnace of a substrate processing apparatus in one embodiment.

[0011] Figure 2 yes Figure 1 A rough cross-sectional view along line AA in the diagram.

[0012] Figure 3 This is a schematic structural diagram of the controller of the substrate processing apparatus in one embodiment, and is a block diagram representing the control system of the controller.

[0013] Figure 4 This is a diagram illustrating an example of a substrate processing step in one embodiment. Detailed Implementation

[0014] The following is mainly based on Figures 1-4 One aspect of this disclosure will be described. Furthermore, the accompanying drawings used in the following description are schematic. The dimensional relationships and scales of the elements shown in the drawings may not necessarily correspond to reality. The dimensional relationships and scales of the elements may also not be consistent across multiple drawings.

[0015] (1) Structure of the substrate processing device

[0016] The substrate processing apparatus 10 includes a processing furnace 202 equipped with a heater 207, which serves as a heating unit (heating mechanism, heating system). The heater 207 is cylindrical in shape and is vertically mounted and fixed by a heater base (not shown) that serves as a holding plate.

[0017] Inside the heater 207, an outer tube 203 constituting the reaction tube (i.e., the reaction vessel and processing vessel) is arranged concentrically with the heater 207. The outer tube 203 is made of heat-resistant materials such as quartz and silicon carbide (SiC). The outer tube 203 is formed into a cylindrical shape that is closed at the top and open at the bottom. Below the outer tube 203, a manifold 209 (hereinafter referred to as MF209) is arranged concentrically with the outer tube 203. MF209 is made of metal such as stainless steel. MF209 is formed into a cylindrical shape that is open at both the top and bottom. An O-ring 220a, serving as a sealing member, is provided between the upper end of MF209 and the outer tube 203. MF209 is supported by the heater base, thereby ensuring that the outer tube 203 is vertically mounted and fixed.

[0018] 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 into a cylindrical shape that is closed at the top and open at the bottom. The processing vessel (i.e., the reaction vessel) is mainly composed of the outer tube 203, the inner tube 204, and MF209. A processing chamber 201 is formed in the hollow part of the processing vessel (i.e., inside the inner tube 204).

[0019] The processing chamber 201 is configured to accommodate a multi-layered arrangement of wafers 200, which serve as substrates, in a horizontal orientation in the vertical direction via a boat 217, which serves as a support member.

[0020] Inside the processing chamber 201, nozzles 410, 420, and 430 are provided, penetrating the side wall of MF209 and the inner tube 204. Gas supply pipes 310, 320, and 330 are respectively connected to the nozzles 410, 420, and 430. However, the processing furnace 202 of this embodiment is not limited to the above-described manner.

[0021] Mass flow controllers (MFCs) 312, 322, and 332, serving as flow controllers (flow control units), are sequentially installed from the upstream side of gas supply pipes 310, 320, and 330, respectively. Valves 314, 324, and 334, serving as on / off valves, are also installed in gas supply pipes 310, 320, and 330, respectively. Gas supply pipes 510, 520, and 530, supplying inert gas, are connected downstream of valves 314, 324, and 334 in gas supply pipes 310, 320, and 330, respectively. MFCs 512, 522, and 532, serving as flow controllers (flow control units), and valves 514, 524, and 534, serving as on / off valves, are sequentially installed from the upstream side of gas supply pipes 510, 520, and 530, respectively.

[0022] Nozzles 410, 420, and 430 are respectively connected to the front ends of gas supply pipes 310, 320, and 330. Nozzles 410, 420, and 430 are configured as L-shaped nozzles. The horizontal portions of nozzles 410, 420, and 430 penetrate the side wall of MF209 and the inner tube 204. The vertical portions of nozzles 410, 420, and 430 are located inside the preparation chamber 201a. The preparation chamber 201a has a channel shape (groove shape) that protrudes radially outward from the inner tube 204 and extends vertically. The vertical portions of nozzles 410, 420, and 430 are positioned upward along the inner wall of the inner tube 204 within the preparation chamber 201a (above the arrangement direction of the wafers 200).

[0023] Nozzles 410, 420, and 430 are configured to extend from the lower region of the processing chamber 201 to the upper region of the processing chamber 201. Multiple gas supply holes 410a, 420a, and 430a are respectively provided in the nozzles 410, 420, and 430 at positions opposite to the wafer 200. Processing gas is supplied to the wafer 200 from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430. Multiple gas supply holes 410a, 420a, and 430a are provided from the lower to the upper part of the inner tube 204. Each gas supply hole 410a, 420a, and 430a has the same opening area. Furthermore, the gas supply holes 410a, 420a, and 430a are arranged at the same spacing. However, the gas supply holes 410a, 420a, and 430a are not limited to the above configuration. For example, the opening areas of the gas supply holes 410a, 420a, and 430a can be gradually increased from the lower part to the upper part of the inner tube 204. This makes the gas flow rate supplied to the wafer 200 from the gas supply holes 410a, 420a, and 430a more uniform.

[0024] Multiple gas supply holes 410a, 420a, and 430a of nozzles 410, 420, and 430 are provided from the lower to the upper part of the wafer boat 217. Therefore, the processing gas supplied to the processing chamber 201 from the gas supply holes 410a, 420a, and 430a of nozzles 410, 420, and 430 is supplied to the entire area of ​​the wafer 200 housed from the lower to the upper part of the wafer boat 217. The nozzles 410, 420, and 430 can be configured to extend from the lower region to the upper region of the processing chamber 201; preferably, they are configured to extend to near the top of the wafer boat 217.

[0025] The first material is supplied from the gas supply pipe 310 into the processing chamber 201 via MFC 312, valve 314, and nozzle 410. Furthermore, in this disclosure, the first material is also referred to as raw material, raw agent, or source. When the first material is in a gaseous state, the gaseous first material is also referred to as first gas, raw material gas, or source gas, etc.

[0026] The second material is supplied into the processing chamber 201 from the gas supply pipe 320 via MFC 322, valve 324, and nozzle 420. Furthermore, in this disclosure, the second material is also referred to as a reactant, reactant, or reactant. When the second material is in a gaseous state, the gaseous second material is also referred to as a second gas, reactant gas, or reactant gas, etc.

[0027] A third material is supplied into the processing chamber 201 from the gas supply pipe 330 via MFC 332, valve 334, and nozzle 430. Furthermore, in this disclosure, the third material is also referred to as a dopant, additive, or similar material. When the third material is in a gaseous state, it is also referred to as a third gas, doped gas, or additive gas.

[0028] In this disclosure, the term "agent" as used herein includes at least one of gaseous and liquid substances. Liquid substances include mist substances. That is, a modifier may contain gaseous substances, liquid substances such as mist substances, or both.

[0029] Nitrogen (N2) gas, for example, is supplied as an inert gas to the processing chamber 201 through gas supply pipes 510, 520, and 530 via MFCs 512, 522, and 532, valves 514, 524, and 534, and nozzles 410, 420, and 430, respectively. An example of using N2 gas as an inert gas will be described below. In this disclosure, in addition to N2 gas, rare gases such as Ar, He, Ne, or Xe gas may also be used as the inert gas.

[0030] When the first material flows through the gas supply pipe 310, the first material supply system (first gas supply system) mainly consists of the gas supply pipe 310, MFC 312, and valve 314; however, nozzle 410 can also be included in the first material supply system. When the second material flows through the gas supply pipe 320, the second material supply system (second gas supply system) mainly consists of the gas supply pipe 320, MFC 322, and valve 324; however, nozzle 420 can also be included in the second material supply system. When the third material flows through the gas supply pipe 330, the third material supply system (third gas supply system) mainly consists of the gas supply pipe 330, MFC 332, and valve 334; however, nozzle 430 can also be included in the conditioning agent supply system. The first material supply system, the second material supply system, and the third material supply system constitute the processing gas supply system. Nozzles 410, 420, and 430 can also be included in the processing gas supply system. The inert gas supply system is mainly composed of gas supply pipes 510, 520, 530, MFC 512, 522, 532 and valves 514, 524, 534.

[0031] In addition, a storage section 701 for storing the first material can be provided in the gas supply pipe 310, and a valve 702 can be provided on the rear section (i.e., the processing chamber 201) side of the storage section 701.

[0032] In this embodiment, an annular longitudinal space is defined by the inner wall of the inner tube 204 and the ends of the multiple wafers 200. Gas is pumped into the inner tube 204 through nozzles 410, 420, and 430 disposed in the preparation chamber 201a within the annular longitudinal space. Then, gas is ejected into the inner tube 204 from multiple gas supply holes 410a, 420a, and 430a provided at positions opposite to the wafers 200 on the nozzles 410, 420, and 430. More specifically, gas is ejected from the gas supply holes 410a of the nozzle 410, 420a of the nozzle 420, and 430a of the nozzle 430 in a direction parallel to the surface of the wafers 200.

[0033] The exhaust port (vent) 204a is a through-hole formed on the side wall of the inner tube 204, opposite to the nozzles 410, 420, and 430. The exhaust port 204a is, for example, a narrow, slit-like through-hole elongated in the vertical direction. Gas supplied to the processing chamber 201 from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430 and flowing over the surface of the wafer 200 flows through the exhaust port 204a in the gap formed between the inner tube 204 and the outer tube 203 (i.e., the exhaust path 206). Then, the gas flowing into the exhaust path 206 flows through the exhaust pipe 231 and is discharged outside the processing furnace 202.

[0034] The vent 204a is positioned opposite to the multiple wafers 200. 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 through the vent 204a into the exhaust path 206. The vent 204a is not limited to being a slit-shaped through-hole; it can also be composed of multiple holes.

[0035] An exhaust pipe 231 for venting the atmosphere inside the processing chamber 201 is connected to the exhaust port 231a of MF209. From the upstream side, the exhaust pipe 231 is sequentially connected to a pressure sensor 245 (a pressure detector, or pressure sensing unit) for detecting the pressure inside the processing chamber 201, an APC (Auto Pressure Controller) valve 243, and a vacuum pump 246 (a vacuum venting device). The APC valve 243 can perform vacuum venting and stop vacuum venting within the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating. Furthermore, the pressure inside the processing chamber 201 can be adjusted by regulating the valve opening of the APC valve 243 while the vacuum pump 246 is operating. The exhaust system mainly consists of the exhaust port 204a, exhaust path 206, exhaust pipe 231, APC valve 243, and pressure sensor 245. It is also possible to include the vacuum pump 246 in the exhaust system.

[0036] A sealing cover 219 (hereinafter also referred to as SC219) is provided below MF209, which can airtightly seal the lower opening of MF209. SC219 is configured to abut against the lower end of MF209 from the lower side in the vertical direction. SC219 is made of metal such as SUS and is formed in a disk shape. An O-ring 220b, which abuts against the lower end of MF209, is provided on the upper surface of SC219 as a sealing member. On the opposite side of the processing chamber 201 in SC219, a rotation mechanism 267 is provided to rotate the crystal boat 217 that houses the wafer 200. The rotation shaft 255 of the rotation mechanism 267 passes through SC219 and is connected to the crystal boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the crystal boat 217. SC219 is configured to move vertically upwards and downwards via a crystal boat lift 115 (hereinafter also referred to as BE115), which is vertically installed outside the outer tube 203 as a lifting mechanism. BE115 is configured to move the crystal boat 217 in and out of the processing chamber 201 by raising and lowering SC219. BE115 is configured as a transport device (i.e., a transport mechanism and transport system) for transporting the crystal boat 217 and the wafer 200 housed in the crystal boat 217 in and out of the processing chamber 201.

[0037] The crystal boat 217 is configured such that multiple wafers 200, for example 25 to 200 wafers 200, are arranged horizontally and aligned with each other at their centers in a vertically spaced manner. The crystal boat 217 is made of a heat-resistant material such as quartz or SiC. A dummy substrate 218 is horizontally supported in multiple layers at the bottom of the crystal boat 217. The dummy substrate 218 is made of a heat-resistant material such as quartz or SiC. With this structure, heat from the heater 207 is difficult to transfer to the SC219 side. However, this embodiment is not limited to the above method. For example, a heat insulation cylinder may be provided at the bottom of the crystal boat 217 instead of a dummy substrate 218. The heat insulation cylinder is a cylindrical component made of a heat-resistant material such as quartz or SiC.

[0038] like Figure 2 As shown, a temperature sensor 263, serving as a temperature detector, is installed inside the inner tube 204. The substrate processing apparatus 10 is configured to adjust the electrical current supplied to the heater 207 based on the temperature information detected by the temperature sensor 263, thereby achieving a desired temperature distribution within the processing chamber 201. The temperature sensor 263, like the nozzles 410, 420, and 430, is configured in an L-shape and is installed along the inner wall of the inner tube 204.

[0039] like Figure 3 As shown, the controller 121, serving as the control unit (control unit), is configured as a computer having a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are connected to the CPU 121a via an internal bus in a manner capable of data exchange. An input / output device 122, such as a touch panel, is connected to the controller 121. Furthermore, the board processing apparatus can be configured to have one control unit or multiple control units. That is, control for the processing sequence described later can be performed using one control unit or multiple control units. Multiple control units can be configured as a control system interconnected via a wired or wireless communication network, or control for the processing sequence described later can be performed as a whole control system. In this specification, the term "control unit" is used to refer not only to cases including a single control unit but also to cases including multiple control units and control systems composed of multiple control units.

[0040] The storage device 121c is configured, for example, as a flash memory or a hard disk drive (HDD). Within the storage device 121c, a control program for controlling the operation of the substrate processing apparatus and a process flow describing the manufacturing method (substrate processing method) for the semiconductor device (described later) are stored in a readable manner. The process flow is a combination of steps in the semiconductor device manufacturing method (substrate processing method) described later, which enables the controller 121 to execute the various processes (steps) to obtain a predetermined result, and functions as a program. Hereinafter, the process flow and control program are simply referred to as a program. In this specification, when the term "program" is used, there may be cases where only a process flow unit is included, cases where only a control program unit is included, or cases where a combination of a process flow and a control program is included. RAM 121b is configured as a storage area for temporarily storing programs and data read by the CPU 121a.

[0041] I / O port 121d is connected to the aforementioned MFC312, 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, rotating mechanism 267, and BE115.

[0042] CPU 121a is configured to read and execute a control program from storage device 121c, and to read process information from storage device 121c based on operation commands input from input / output device 122. CPU 121a is configured to control specific actions according to the read process information. Specific actions include: various gas flow adjustment actions performed by MFC312, 322, 332, 512, 522, and 532; opening and closing actions of valves 314, 324, 334, 514, 524, 534, and 702; gas storage action to storage unit 701 via valve 702; opening and closing actions of APC valve 243; pressure adjustment action based on pressure sensor 245 via APC valve 243; temperature adjustment action of heater 207 based on temperature sensor 263; starting and stopping of vacuum pump 246; rotation and rotation speed adjustment actions of crystal boat 217 performed by rotating mechanism 267; lifting and lowering action of crystal boat 217 performed by BE115; and receiving action of wafer 200 into crystal boat 217.

[0043] The controller 121 can be configured by installing the program stored in an external storage device (such as a hard disk, CD, DVD, or semiconductor memory such as flash memory or memory card) 123 into a computer. Storage device 121c and external storage device 123 constitute a computer-readable storage medium. Hereinafter, they will also be collectively referred to as storage media. In this specification, the storage medium may consist only of storage device 121c, only of external storage device 123, or both storage device 121c and external storage device 123. Providing the program (program product) to the computer may also be done without using external storage device 123, but using a communication unit such as the Internet or a dedicated line.

[0044] (2) Substrate processing process

[0045] As a step in the manufacturing process of semiconductor devices, using Figure 4 An example of a process for forming a silicon nitride (SiN) film on a wafer 200, which serves as a charge trapping film for example, 3D NAND, will be described. The process of forming the SiN film is performed using the processing furnace 202 of the substrate processing apparatus 10 described above. Furthermore, in this embodiment, an example of a substrate (wafer) with grooves, holes, or other recesses on its surface will be described as the wafer 200. In the following description, the operation of each component of the substrate processing apparatus 10 is configured to be controllable by the controller 121.

[0046] The substrate processing step (semiconductor device manufacturing step) in this embodiment includes the following steps:

[0047] (a) A process of supplying a first material to wafer 200, wherein the first material comprises a first element constituting a film;

[0048] (b) The process of supplying a second material to wafer 200, wherein the second material comprises a second element constituting the film;

[0049] (c) The process of supplying a third material to wafer 200, wherein the third material comprises an element added to the film, namely a third element; and

[0050] (d) The process of forming a film containing the first element, the second element and the third element on wafer 200 by performing (a), (b) and (c) a specified number of times.

[0051] 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.

[0052] In this disclosure, the processing sequence described above includes the sequences shown in (A) to (G) below. The same expressions as those below are also used in the description of other embodiments.

[0053] (A) (First material → Second material → Third material) × Xa

[0054] (B) (First material → Third material → Second material) × Xb

[0055] (C) (Second material → Third material → First material) × Xc

[0056] (D) (Third material → Second material → First material) × Xd

[0057] (E)(First Material + Second Material + Third Material) × Xe

[0058] (F)(First material + Second material → Third material) × Xf

[0059] (G) (Second material + Third material → First material) × Xg

[0060] Where Xa~Xg are natural numbers (integers of 1 or 2 or higher). “→” means supplying different types of materials sequentially, and “+” means supplying different types of materials simultaneously. Supplying different types of materials simultaneously means that there are overlapping periods during which different types of materials are supplied. In addition, a process for removing material present on wafer 200 (also known as a purging process) can be performed between the “→” signs.

[0061] In this specification, the term "wafer" can refer to either "the wafer itself" or "a laminate of a wafer and a specified layer or film formed on its surface." Similarly, the term "surface of a wafer" can refer to either "the surface of the wafer itself" or "the surface of a specified layer or film formed on the wafer." When described as "forming a specified layer on the wafer," it can mean either forming the specified layer directly on the surface of the wafer itself or forming the specified layer on top of a layer formed on the wafer. The term "substrate" is also synonymous with the term "wafer" in this specification.

[0062] (The choice of the third element)

[0063] The selection of the third element is then made. The doping element (i.e., the third element) may be selected, for example, based on the following criteria A) to D).

[0064] A) Electronegativity

[0065] B) Atomic size

[0066] C) Coordination number

[0067] D) Types of elements

[0068] (A: Selection based on electronegativity)

[0069] Here, the selection of the third element based on electronegativity when the film formed on wafer 200 is the following type of film will be explained. The case in which 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 explained.

[0070] The third element added to the film can be selected based on the relationship between the electronegativity of the third element and the electronegativity of the second element, and the relationship between the electronegativity of the first element and the electronegativity of the second element. For example, the third element can be selected such that 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 selecting the third element according to this relationship, 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, and the charge of the first element is slightly biased towards the positive. As a result, an energy level capable of trapping electrons is realized around the first element. Utilizing this effect, the charge trapping capability of a semiconductor device can be improved by forming a charge trapping layer.

[0071] Preferably, the third element is an element with a lower electronegativity than the second element. More preferably, the third element is an element with a lower electronegativity than the first element. By selecting the third element based on the electronegativity relationship of each element, the aforementioned effects can be further achieved.

[0072] (B: Selection based on atomic size)

[0073] When selecting the third element based on atomic size, the atomic size of the third element is preferably similar to that of the first element. In other words, the atomic size of the third element can be said to be closer to that of the first element than the atomic size of the second element. The closer the atomic size of the third element is to that of the first element, the more effectively the atomic filling rate in the membrane can be reduced. By reducing the atomic filling rate in the membrane, the space for trapping (capturing) electrons can be increased.

[0074] Preferably, the third element is an element whose atomic size is larger than but close to that of the first element. More preferably, the third element is an element whose atomic size is larger than that of the second element but smaller than that of an element in the same group as the first element but different from it. For example, when the first element is Si, the second element is N, and the third element is an element whose atomic size is larger than that of N but smaller than that of tin (Sn), a Group 14 element in the same group as Si, the third element can form the same four covalent bonds as Si, thus replacing Si with the third element. This increases the space for electron trapping; in other words, it increases the amount of electrons trapped.

[0075] (C: Selection based on coordination number)

[0076] The case where the film is composed of SiN will be explained. The third element is preferably an element capable of 3- or 4-coordinate. 3-coordinate means the third element has 3 ligands. 4-coordinate means the third element has 4 ligands. The ability of the third element to be 3-coordinate means that the third element can form 3 ligands. The ability of the third element to be 4-coordinate means that the third element can form 4 ligands. Furthermore, the bond in the ligand is at least one of a covalent bond, a coordinate bond, and an ionic bond. Having a third element capable of 3- or 4-coordinate increases the space for electron trapping. In other words, it increases the amount of electrons trapped. Preferably, the third element is capable of 3-coordinate. When comparing 4-coordinate elements with 3-coordinate elements, 3-coordinate elements sometimes increase the space for electron trapping.

[0077] (D: Selection based on the type of element)

[0078] The case where the film is composed of SiN will be explained. Preferably, the third element is a metallic element. Having a metallic third element provides the same effect as described above. Preferably, the third element is at least one element from the third, fourth, and fifth periods of the periodic table. More preferably, the third element is at least one element from the third, fourth, and fifth periods 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, increasing the amount of electrons captured. 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 any one of Zn, Ga, and In. By using these elements as the third element, more electrons can be captured. That is, the amount of electrons captured can be increased.

[0079] A preparation process is performed to supply a third material to wafer 200, wherein the third material includes a third element selected according to the selection criteria described above.

[0080] (Moving in the wafer)

[0081] When loading multiple wafers 200 into the crystal boat 217, such as Figure 1 As shown, a crystal boat 217 supporting multiple wafers 200 is lifted by BE115 and moved into the processing chamber 201. Then, the crystal boat 217 supporting multiple wafers 200 is housed in a processing container. In this state, SC219 closes the lower opening of the outer tube 203 via the O-ring 220.

[0082] (Pressure and temperature adjustment)

[0083] Vacuum pump 246 vents the processing chamber 201 to achieve the desired pressure within the chamber (i.e., the space containing the wafer 200). The pressure within the processing chamber 201 is measured by pressure sensor 245. Based on the pressure information measured by pressure sensor 245, APC valve 243 is controlled via feedback (pressure adjustment). Vacuum pump 246 remains operational until processing of the wafer 200 is complete. Heater 207 heats the processing chamber 201 to achieve the desired temperature. Based on the temperature information detected by temperature sensor 263, the electrical current supplied to heater 207 is controlled via feedback (temperature adjustment) to achieve the desired temperature distribution within the processing chamber 201. Heating of the processing chamber 201 by heater 207 continues until processing of the wafer 200 is complete.

[0084] (Film forming process)

[0085] Next, the film-forming process is performed. This process includes: a first material supply process, a purging process, a second material supply process, a purging process, a third material supply process, a purging process, and a process for determining whether these processes have been performed a specified number of times (n times, where n is an integer of 1 or 2 or more). Each process is described below.

[0086] (First material supply process: First process)

[0087] Controller 121 opens valve 314, allowing the first material to flow through gas supply pipe 310. After flow adjustment by MFC 312, the first material is supplied into processing chamber 201 from gas supply port 410a of nozzle 410. The first material supplied into processing chamber 201 is discharged from exhaust pipe 231. Thus, the first material is supplied to wafer 200. At this time, controller 121 can open valve 514, allowing an inert gas such as N2 gas to flow through gas supply pipe 510. The N2 gas flowing through gas supply pipe 510, after flow adjustment by MFC 512, is supplied into processing chamber 201 along with the first material. The N2 gas supplied into processing chamber 201 is discharged from exhaust pipe 231. At this time, to prevent the first material from entering nozzles 420 and 430, controller 121 can open valves 524 and 534, allowing N2 gas to flow through gas supply pipes 520 and 530. N2 gas is supplied to the processing chamber 201 via gas supply pipes 320 and 330 and nozzles 420 and 430, and is then discharged from the exhaust pipe 231.

[0088] At this time, controller 121 adjusts APC valve 243 to bring the pressure inside processing chamber 201 to, for example, a range of 1 to 3990 Pa. The raw material supply flow rate controlled by MFC 312 is, for example, 1 to 2000 sccm, preferably 10 to 1000 sccm. Here, the supply conditions of the first material are set such that the exposure of the first material to the wafer 200 is greater than the exposure of the third material. Furthermore, the exposure of the first material in this disclosure is, for example, the product of the partial pressure of the raw material in processing chamber 201 and the supply time of the raw material to processing chamber 201 (partial pressure × time). The supply flow rates of N2 gas controlled by MFCs 512, 522, and 532 are, for example, in the range of 0.1 to 5.0 slm. At this time, the temperature of heater 207 is set to bring the temperature of wafer 200 to, for example, a range of 250 to 800°C, preferably 600 to 700°C. Furthermore, the exposure amount of the first material in this disclosure can 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 × 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 × supply time), or the product of the partial pressure (total pressure) in the processing chamber 201 and the supply flow rate of the first material into the processing chamber 201 and the supply time (partial pressure (total pressure) × supply flow rate × supply time). The supply flow rate of the first material into the processing chamber 201 is affected by the volume of the processing container, the pattern formed in the recess of the wafer 200, etc. Therefore, the exposure amount of the first material is preferably the product of the partial pressure in the processing chamber 201 and the supply time of the raw material into the processing chamber 201. In addition, the numerical range expression "1~3990Pa" in this disclosure means that the lower limit and the upper limit are included in the range. Therefore, for example, "1~3990Pa" means "more than 1Pa and less than 3990Pa". Other numerical ranges are the same as described above.

[0089] In this disclosure, the exposure amount of the first material to the wafer 200 can also be referred to as the amount of gas molecules adsorbed on the surface of the wafer 200. As mentioned above, this amount of adsorption can be adjusted, for example, by 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 × time).

[0090] In order to make the exposure amount (adsorption amount) of the first material in this disclosure greater than the exposure amount (adsorption amount) of the third material, it can be adjusted by making at least one of the partial pressure, total pressure, supply flow rate and supply time related to the exposure amount of the first material 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.

[0091] Alternatively, the first material can be stored in the storage unit 701 and supplied from the storage unit 701 to the processing chamber 201. When supplying the first material stored in the storage unit 701 to the processing chamber 201, the time for supplying the first material to the processing chamber 201 may sometimes be shorter than either the time for supplying the second material to the processing chamber 201 or the time for supplying the third material. In this case, for example, the exposure amounts of the first, second, and third materials can be 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 to the processing chamber 201 is greater than the product of the partial pressure (total pressure) of the second (third) material in the processing chamber 201 and the supply time of the second (third) material to the processing chamber 201. Furthermore, in the first material supply process, the supply of the first material to the processing chamber 201 can be performed not only once, but also multiple times. When supplying the first material to the processing chamber 201 multiple times, the supply of the first material to the processing chamber 201 is stopped between the predetermined number of times and the next time. When supplying the first material to the processing chamber 201 multiple times, the first material accumulated in the storage section 701 can be supplied to the processing chamber 201 at least once. For example, when supplying the first material to the processing chamber 201 more than twice, in the first instance, the first material accumulated in the storage section 701 is supplied to the processing chamber 201, and in the second instance, the first material is supplied to the processing chamber 201 when the storage section 701 is empty. Furthermore, the supply of the first material to the processing chamber 201 is stopped between the first and second instances. The processing chamber 201 can be vented (pressure reduced) in conjunction with stopping the supply of the first material, and an inert gas can also be supplied to the processing chamber 201 in conjunction with the venting. Furthermore, the supply and cessation of the first material supply to the processing chamber 201 can be controlled, for example, by opening and closing the valve 702.

[0092] The first material (raw material) supplied to wafer 200 includes, for example, the main element constituting the film formed on wafer 200. The first material contains a first element. Preferably, the first element is a group 14 element. The main element of the first material can be, for example, Si. As the first material, a silane-based gas containing Si can be used, for example. As a silane-based gas, a gas containing Si and a halogen (i.e., a halosilane gas) can be used, for example. Halogens include chlorine (Cl), fluorine (F), bromine (Br), and iodine (I), etc. As a halosilane gas, a chlorosilane gas containing Si and Cl can be used, for example.

[0093] As raw materials, chlorosilane gases such as monochlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), tetrachlorosilane (SiCl4), hexachlorodisilane (Si2Cl6, abbreviated as HCDS), and octachlorotrisilane (Si3Cl8) can be used. One or more of these can be used as the primary material.

[0094] In addition to chlorosilane gas, other fluorosilane gases such as tetrafluorosilane (SiF4) gas and difluorosilane (SiH2F2) gas, bromosilane gases such as tetrabromosilane (SiBr4) gas and dibromosilane (SiH2Br2) gas, and iodosilane gases such as tetraiodosilane (SiI4) gas and diiodosilane (SiH2I2) gas can also be used as the first material. One or more of these gases can be used as the first material.

[0095] In addition to these, gases containing Si and amino groups (i.e., aminosilane gases) can also be used as primary materials. An amino group is a monovalent functional group formed by removing hydrogen (H) from ammonia, primary amines, or secondary amines, and can be represented by -NH2, -NHR, and -NR2. Furthermore, R represents an alkyl group, and the two Rs in -NR2 can be the same or different.

[0096] As a first material, for example, tetra(dimethylamino)silane (Si[N(CH3)2]4) gas, tri(dimethylamino)silane (Si[N(CH3)2]3H) gas, bis(diethylamino)silane (Si[N(C2H5)2]2H2) gas, bis(tert-butylamino)silane (SiH2[NH(C4H9)]2) gas, and (diisopropylamino)silane (SiH3[N(C3H7)2]) gas, etc., can be used as aminosilane gases. One or more of these can be used as the first material.

[0097] In this disclosure, an example using HCDS gas as the first material is described. When HCDS gas is used as the first material, a Si-containing layer of a predetermined thickness containing Cl can be formed as the first layer on the outermost surface of the wafer 200. The Si-containing layer containing Cl can be formed by: physical adsorption or chemical adsorption of molecules of the first material on the outermost surface of the wafer 200; physical adsorption or chemical adsorption of molecules of a substance (also called a decomposition product) formed by the decomposition of at least a portion of the molecules of the first material; Si deposition caused by the thermal decomposition of the first material, etc. The decomposition product when using HCDS as the first material is, for example, SiClx. Here, x is 2, 3, or 4. Furthermore, the Si-containing layer containing Cl can be an adsorption layer (physical adsorption layer or chemical adsorption layer) of chlorosilane gas molecules or molecules of a substance formed by the decomposition of a portion of chlorosilane gas, or it can be a Si deposition layer containing Cl. When the above-mentioned chemical adsorption layer or the above-mentioned deposition layer is formed on the outermost surface of the wafer 200, the Si contained in the chlorosilane gas is adsorbed on the outermost surface of the wafer 200. In this disclosure, the Si-containing layer containing Cl is also simply referred to as the Si-containing layer.

[0098] (Purge process (residual gas removal))

[0099] After a predetermined time (e.g., 1 to 60 seconds) has elapsed since the start of the first material supply, controller 121 closes valve 314 (or valve 702) of gas supply pipe 310, stopping the supply of the first material. That is, the time for supplying the first material to wafer 200 is, for example, within the range of 1 to 60 seconds. At this time, with APC valve 243 of exhaust pipe 231 open, controller 121 uses vacuum pump 246 to vent the processing chamber 201, removing any unreacted first material remaining in the processing chamber 201 and any first material that participated in layer formation. In other words, controller 121 vents the atmosphere inside the processing chamber 201. At this time, controller 121 can maintain the supply of N2 gas to the processing chamber 201 with valves 514, 524, and 534 open. N2 gas functions not only as a suppressant gas to enter nozzles 410, 420, and 430, but also as a purging gas. When N2 gas is supplied as a purging gas, the effect of removing unreacted first material remaining in the processing chamber 201 and first material that has participated in layer formation from the processing chamber 201 can be improved.

[0100] (Second material supply: Second process)

[0101] After removing residual gas from processing chamber 201, controller 121 opens valve 324, allowing the second material to flow within gas supply pipe 320. The second material, after flow rate adjustment by MFC 322, is supplied into processing chamber 201 from gas supply port 420a of nozzle 420. The second material supplied into processing chamber 201 is discharged from exhaust pipe 231. At this time, the second material is supplied to wafer 200. Meanwhile, controller 121 maintains the supply of N2 gas into gas supply pipes 510, 520, and 530 with valves 514, 524, and 534 open. The flow rate of N2 gas flowing in gas supply pipes 510, 520, and 530 is adjusted by MFCs 512, 522, and 532 respectively. The N2 gas flowing in gas supply pipe 520, along with the second material, is supplied into processing chamber 201 via gas supply pipe 320 and nozzle 420, and then discharged from exhaust pipe 231. N2 gas flowing in gas supply pipe 530 is supplied to processing chamber 201 via gas supply pipe 330 and nozzle 430, and then discharged from exhaust pipe 231. N2 gas flowing in gas supply pipe 510 is supplied to processing chamber 201 via gas supply pipe 310 and nozzle 410, and then discharged from exhaust pipe 231. This prevents the second material from entering nozzle 410.

[0102] At this time, controller 121 adjusts APC valve 243 to make the pressure in processing chamber 201, for example, within the range of 1 to 13300 Pa (e.g., 5000 Pa). The supply flow rate of the second material controlled by MFC 322 is, for example, within the range of 1 to 50 slm, preferably within the range of 15 to 40 slm. The supply flow rate of N2 gas controlled by MFCs 512, 522, and 532 is, for example, within the range of 0.1 to 5.0 slm.

[0103] Furthermore, the amount of exposure (adsorption) of the second material to the wafer 200 is preferably the amount at which the adsorption of the molecules of the second material on the wafer 200 reaches saturation. In other words, the amount of exposure (adsorption) of the second material to the wafer 200 is preferably the amount at which the adsorption of the molecules of the second material on the wafer 200 reaches saturation.

[0104] The second material contains a second element. Preferably, the second element is the fifteenth element. As the second material supplied to wafer 200, for example, an N- and H-containing gas can be used as a nitriding gas (nitriding agent). 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 NH bonds.

[0105] As a second material, nitrogen-hydrogen gases such as ammonia (NH3), diazoxide (N2H2), hydrazine (N2H4), and N3H8 can be used. More than one of these gases can be used as a second material.

[0106] In addition to these, gases containing N, carbon (C), and H can also be used as a second material. For example, amine gases and organic hydrazine gases can be used as N, C, and H gases. A gas containing N, C, and H is a gas containing N, a gas containing C, a gas containing H, and a gas containing both N and C.

[0107] As a second material, for example, ethylamine gases such as monoethylamine (C2H5NH2), diethylamine ((C2H5)2NH), and triethylamine ((C2H5)3N), methylamine gases such as monomethylamine (CH3NH2), dimethylamine ((CH3)2NH), and trimethylamine ((CH3)3N), and organohydrazine gases such as monomethylhydrazine ((CH3)HN2H2), dimethylhydrazine ((CH3)2N2H2), and trimethylhydrazine ((CH3)2N2(CH3)H) can be used. One or more of these can be used as a second material. Furthermore, these gases are also called amine gases.

[0108] (Purge process: to remove residual gases)

[0109] After a predetermined time (e.g., 1 to 1200 seconds) elapses from the start of the second material supply, controller 121 closes valve 324 of gas supply pipe 320, stopping the supply of the second material. Then, through a process similar to the purging procedure described above, unreacted or partially reacted second material and reaction byproducts remaining in processing chamber 201 are removed from processing chamber 201. That is, controller 121 vents the atmosphere in processing chamber 201.

[0110] (The supply process of the third material: the third process)

[0111] Controller 121 opens valve 334, allowing the third material to flow within gas supply pipe 330. After flow adjustment by MFC 332, the third material is supplied to processing chamber 201 from gas supply port 430a of nozzle 430. The third material supplied to processing chamber 201 is discharged from exhaust pipe 231. At this time, the third material is supplied to wafer 200. Additionally, controller 121 may also open valve 534, allowing an inert gas such as N2 gas to flow within gas supply pipe 530. The N2 gas flowing within gas supply pipe 530, after flow adjustment by MFC 532, is supplied to processing chamber 201 along with the third material. The N2 gas supplied to processing chamber 201 is discharged from exhaust pipe 231. At this time, to prevent the third material from entering nozzles 410 and 420, controller 121 may open valves 512 and 524, allowing N2 gas to flow within gas supply pipes 510 and 520. N2 gas is supplied into the processing chamber 201 via gas supply pipes 310 and 320 and nozzles 410 and 420, and is discharged from the exhaust pipe 231.

[0112] At this time, controller 121 adjusts APC valve 243 to set the pressure in processing chamber 201 to, for example, a range of 1 to 3990 Pa (e.g., 1000 Pa). The supply flow rate of the third material controlled by MFC 332 is, for example, a flow rate in the range of 0.005 to 3.0 slm. Here, controller 121 adjusts the pressure in processing chamber 201 and the supply flow rate and supply time of the third material into processing chamber 201 so that the exposure of the third material to wafer 200 is a predetermined exposure amount. Furthermore, the exposure amount of the third material in this disclosure is, for example, calculated by the product of the partial pressure of the third material in processing chamber 201 and the supply time of the third material into processing chamber 201 (partial pressure × time). The exposure amount of the third material is less than the exposure amount of the first material and the exposure amount of the second material. In order to suppress the third material from entering each nozzle 410, 420, the supply flow rate of N2 gas controlled by MFC 512, 522 is, for example, a flow rate in the range of 0.1 to 5.0 slm. At this time, the temperature of heater 207 is set to a temperature such that the temperature of wafer 200 is, for example, in the range of 250~800°C, preferably 600~700°C.

[0113] As a third material, gases containing chlorides such as aluminum chloride (AlCl3), gallium chloride (GaCl3), indium chloride (InCl3), zinc chloride (ZnCl2), titanium chloride (TiCl4), zirconium chloride (ZrCl4), and hafnium chloride (HfCl4) can be used (i.e., gases of inorganic materials). Alternatively, gases formed by mixing such chlorides with other solvents and then vaporizing them can also be used. Organic gases containing alkyl groups, such as trimethylaluminum (Al(CH3)3), triethylaluminum (Al(C2H5)3), trimethylgallium (Ga(CH3)3), triethylgallium (Ga(C2H5)3), trimethylindium (Ga(CH3)3), triethylindium (In(C2H5)3), dimethylzinc (Zn(CH3)2), diethylzinc (Zn(C2H5)2), tri(dimethylamide)cyclopentadienylhafnium (Hf(C5H5)(N(CH3)2)3) gas, tri(dimethylamide)cyclopentadienylzirconium (Zr(C5H5)(N(CH3)2)3), and tetra(dimethylamide)titanium (Ti((CH3)2N)4), can be used.

[0114] (Purge process: to remove residual gases)

[0115] After a predetermined time (e.g., 1 to 1200 seconds) elapses from the start of the supply of the third material, the controller 121 closes the valve 334 of the gas supply pipe 330, stopping the supply of the third material. Then, through a process similar to the purging procedure described above, the unreacted or partially reacted third material and reaction byproducts remaining in the processing chamber 201 are removed from the processing chamber 201. That is, the controller 121 vents the atmosphere in the processing chamber 201.

[0116] (Number of times specified)

[0117] By sequentially performing the first, second, and third steps described above a predetermined number of times (n times, where n is an integer of 1 or 2 or more), a film of a predetermined thickness containing elements of a first material is formed on wafer 200. For example, a SiN film can be formed on wafer 200. The above cycle is preferably repeated multiple times.

[0118] (Purge and restore atmospheric pressure)

[0119] Controller 121 supplies N2 gas into processing chamber 201 from each of gas supply pipes 510, 520, and 530. The N2 gas supplied into processing chamber 201 is discharged from exhaust pipe 231. N2 gas acts as a purging gas. As a result, processing chamber 201 is purged with inert gas, and residual materials (gases) and reaction byproducts in processing chamber 201 are removed. Afterward, the atmosphere in processing chamber 201 is replaced with inert gas, and the pressure in processing chamber 201 is restored to atmospheric pressure.

[0120] (Moving out the wafer)

[0121] Next, SC219 is lowered via BE115, opening the lower end of the outer tube 203. Then, the processed wafer 200, supported by the wafer boat 217, is moved out of the outer tube 203 from its lower end. Afterward, the processed wafer 200 is removed from the wafer boat 217.

[0122] (3) Effects of this implementation method

[0123] According to this embodiment, one or more of the following effects can be obtained.

[0124] (a) It can improve the charge trapping performance of films formed on wafer 200.

[0125] (b) The difference between the electronegativity of the third element and the second element is greater than the difference between the electronegativity of the first element and 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 by the second element, and the third element can easily 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 by the third element, and the charge of the first element is slightly biased towards the positive. As a result, an energy level capable of trapping electrons is realized around the first element. Utilizing this effect, the charge trapping capability of a semiconductor device can be improved by forming a charge trapping layer.

[0126] (c) The third element is an element with lower electronegativity than the second element, thus, the effect of (b) can be further obtained.

[0127] (d) The atomic size of the third element is closer to that of the first element than that of the second element, thereby reducing the atomic filling rate in the membrane. By reducing the atomic filling rate in the membrane, the space for trapping (capturing) electrons can be increased.

[0128] (e) Preferably, the third element is an element whose atomic size is larger than that of the first element but close to that of the first element. More preferably, the third element is an element whose atomic size is larger than that of the second element but smaller than that 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 electrons trapped can be increased.

[0129] (f) When the film is made of SiN, the third element is an element that can take 3 or 4 coordination positions, thereby increasing the space for capturing electrons of SiN. In other words, the amount of electrons captured can be increased.

[0130] (g) When the film is made of SiN, it is preferable that the third element is a metallic element. Having a metallic third element provides the same effect as described above. More preferably, the metallic element is at least one of zinc (Zn), gallium (Ga), aluminum (Al), and indium (In). More preferably, the third element is at least one of Zn, Ga, and In. More preferably, it is In. With In, the number of trapped electrons can be increased through a mechanism that forms 3-coordinate bonds and allows electrons to enter the remaining electron-free orbitals. When comparing these Zn, Ga, Al, and In elements, the trapping depth (trap depth) follows the relationship Zn < Ga < Al < In, with In having the deepest trapping depth. Increasing the trapping depth improves electron retention performance. Furthermore, compared to other metallic elements (e.g., Hf, Ti), these elements make it difficult for shallow trapping levels to form in the electron-retaining energy levels. Here, a shallow trapped level refers to an energy level close to the conduction band. Even if electrons can be retained at a shallow trapped level, they may sometimes be released due to various factors, becoming a major cause of device performance degradation. On the other hand, it is difficult to form shallow trapped levels for elements such as Zn, Ga, Al, and In. Furthermore, for Al and In, the energy levels near these elements that can trap electrons will form deeper levels than the trapped energy levels of the SiN material itself. Therefore, by forming films using these elements, the electron retention performance of the device can be improved. In addition, a deep level refers to an energy level that is closer to the valence band than the trapped energy levels of the SiN material itself.

[0131] <Other methods of this disclosure>

[0132] The above provides a detailed explanation of the methods used in this disclosure. However, this disclosure is not limited to the methods described above and can be modified in various ways without departing from its core principles.

[0133] For example, in the above embodiments, the case of using a gas containing Si as the first material was described as an example, but this disclosure is not limited thereto. For example, it can sometimes be applied to the processing of a gas containing at least one element from Group 13, Group 14, Group 4, Group 6, and Group 8 as the first material.

[0134] In the above embodiments, the case of using a nitrogen-containing gas as the second material was described as an example, but this disclosure is not limited thereto. For example, an oxygen-containing gas may also be used as the second material to form an oxide film on wafer 200. Examples of oxygen-containing gases include oxygen (O2), water (H2O), hydrogen peroxide (H2O2), nitrous oxide (N2O), nitric oxide (NO), and ozone (O3). A gas obtained by activating or exciting one or more of these gases may also be used as the second material.

[0135] As a second material, a gas containing hydrogen can be used to form a film with the aforementioned element as the main component on wafer 200. Examples of hydrogen-containing gases include hydrogen (H2) gas, deuterium gas, and other gases composed of hydrogen, as well as gases containing mononuclear parent hydrides such as silane-based gases, borane-based gases, phosphine-based gases, and germanane-based gases. As a reactant, a gas obtained by activating or exciting at least one of these gases can be used. Furthermore, silane-based gases include monosilane (SiH4) gas, disilane (Si2H6) gas, and trisilane (Si3H8) gas. Borane-based gases include monoborane (BH3) gas and diborane (B2H6) gas. Phosphine-based gases include phosphine (PH3) gas and diphosphine (P2H6) gas. Germanane-based gases include monogermanane (GeH4) gas, digermanane (Ge2H6) gas, and trigermanane (Ge3H8) gas.

[0136] In the above embodiments, an example of film formation using a batch-type vertical apparatus, i.e., a substrate processing apparatus, that processes multiple substrates at a time has been described. However, this disclosure is not limited to this, and it can also be suitably applied to the case of film formation using a monolithic substrate processing apparatus that processes at least one substrate at a time. In the above embodiments, an example of film formation using a substrate processing apparatus equipped with a hot-wall type processing furnace has been described. This disclosure is not limited to the above embodiments, and it can also be suitably applied to the case of film formation using a substrate processing apparatus equipped with a cold-wall type processing furnace. When using these substrate processing apparatuses, film formation can also be performed using the same processing sequence and processing conditions as in the above embodiments.

[0137] Furthermore, the above-described method illustrates an example of performing the above-described processing sequence within the same processing chamber (in-situ) of the same processing device. This disclosure is not limited to the above-described method; for example, one step and other steps of the above-described processing sequence may be performed separately within different processing chambers (ex-situ) of different processing devices, or separately within different processing chambers of the same processing device.

[0138] The process procedures (i.e., programs that describe the processing steps, processing conditions, etc.) used to form these various thin films are preferably prepared individually (i.e., multiple process procedures are prepared) according to the content of the substrate processing (e.g., the type, composition ratio, film quality, film thickness, processing steps, or processing conditions of the thin film to be formed). Then, preferably, when starting the substrate processing, an appropriate process procedure is selected from the multiple process procedures according to the content of the substrate processing. Specifically, it is preferable to pre-store (install) the multiple process procedures prepared individually according to the content of the substrate processing in the storage device 121c of the substrate processing apparatus via an electrical communication line or a storage medium (e.g., external storage device 123) recording the process procedures. Then, preferably, when starting the substrate processing, the CPU 121a of the substrate processing apparatus selects an appropriate process procedure from the multiple process procedures stored in the storage device 121c according to the content of the substrate processing. With this configuration, thin films of various types, composition ratios, film qualities, and film thicknesses can be formed universally and reproducibly using a single substrate processing apparatus. Because it can reduce the operator's workload (e.g., the input burden of the processing procedure or processing conditions), it can avoid operator errors and enable rapid commencement of substrate processing.

[0139] This disclosure can also be implemented, for example, by changing the process of an existing substrate processing apparatus. When changing the process, the process of this disclosure can also be installed in an existing substrate processing apparatus via an electrical communication line or a storage medium recording the process, or the input / output device of an existing substrate processing apparatus can be operated to change the process itself to the process of this disclosure.

[0140] The above-described embodiments and modifications can be used in appropriate combinations. The processing procedures and conditions can, for example, be the same as those in the above-described embodiments and modifications.

[0141] The embodiments of this disclosure have been described in detail above. However, this disclosure is not limited to the above embodiments, and various modifications can be made without departing from its core essence.

[0142] The disclosure of Japanese Patent Application No. 2024-052683, filed on March 28, 2024, is incorporated herein by reference in its entirety.

[0143] All documents, patent applications and technical standards described in this specification are incorporated herein by reference, which is equivalent to each document, patent application and technical standard being explicitly cited separately.

Claims

1. A substrate processing method comprising the following steps: (a) The process of supplying a first material to a substrate, wherein, The first material contains a first element constituting the membrane; (b) A step of supplying a second material to the substrate, wherein the second material comprises a second element constituting the film; (c) The step of supplying a third material to the substrate, wherein the third material comprises an element added to the film, namely a third element; and (d) The process of forming a membrane comprising the first element, the second element, and the third element by performing (a), (b), and (c) a predetermined number of times. 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.

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

3. The substrate processing method according to claim 1, wherein, The third element is an element with 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 the same as that of the first element.

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

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

7. The substrate processing method according to claim 1, wherein, The third element is an element with a larger atomic size than the second element, but smaller atomic size than 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 that can take 3-coordinate or 4-coordinate.

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

12. The substrate processing method according to any one of claims 1 to 8, wherein, The third element is at least one of the 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 the 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 fourteen 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 the following steps: (a) The process of supplying a first material to a substrate, wherein, The first material contains a first element constituting the membrane; (b) A step of supplying a second material to the substrate, wherein the second material comprises a second element constituting the film; (c) The step of supplying a third material to the substrate, wherein the third material comprises a third element added to the film; and (d) The process of forming a membrane comprising the first element, the second element, and the third element by performing (a), (b), and (c) a predetermined number of times. 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.

19. A program that causes a substrate processing apparatus to execute (a), (b), (c) and (d) via a computer: (a) A process of supplying a first material to a substrate, wherein, The first material contains a first element constituting the membrane; (b) A process of supplying a second material to the substrate, wherein the second material comprises a second element constituting the film; (c) A process of supplying a third material to the substrate, wherein the third material comprises a third element added to the film, and 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) The process of forming a membrane containing the first element, the second element and the third element by performing (a), (b) and (c) a specified number of times.

20. A substrate processing apparatus comprising: The first supply unit supplies the first material to the substrate, wherein... The first material contains a first element constituting the membrane; A second supply unit supplies a second material to the substrate, wherein the second material comprises a second element constituting the film; A third supply unit supplies a third material, wherein the third material comprises an element added to the membrane, namely a third element; and The control unit is configured to control the first supply unit, the second supply unit, and the third supply unit to perform specific processing. 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. The specific processing includes the following: (a) A process of supplying the first material to the substrate; (b) The process of supplying the second material to the substrate; (c) The process of supplying the third material to the substrate; and (d) Performing (a), (b) and (c) a predetermined number of times to form a membrane containing the first element, the second element and the third element.

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