Substrate processing method, method of manufacturing semiconductor device, substrate processing apparatus, and program article

Abstract

The invention relates to a substrate processing method, a method of manufacturing a semiconductor device, a substrate processing apparatus, and a program product. Provided is a technique capable of efficiently performing selective film formation. The method for forming a metal element-containing film on a substrate includes a film forming step of forming a metal element-containing film on a first surface preferentially than on a second surface by performing the following (a) and (b): (a) performing (a1) a step of supplying a first gas containing a metal element to the substrate and (a2) a step of supplying a second gas containing the metal element to the substrate; a step for forming a metal-containing substance containing the metal element on at least a part of the substrate, the substrate having a first surface, which is a surface of a first substance, and a second surface, which is a surface of a second substance different from the first substance; (b) a step of supplying a reaction gas to the substrate, (a) including a period Tc in which (a1) and (a2) are at least partially performed simultaneously, the first gas etches the metal-containing substance at a first rate, and the second gas etches the metal-containing substance at a second rate higher than the first rate.

Description

Technical Field

[0001] This invention relates to substrate processing methods, semiconductor device manufacturing methods, substrate processing apparatus, and process articles. Background Technology

[0002] As a step in the manufacturing process or substrate processing process of a semiconductor device, a process is sometimes performed in which a film is preferentially formed on a certain surface compared to other surfaces, i.e., selective film formation (see, for example, Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: International Publication No. 2018 / 179354 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] This invention provides a technique for efficient selective film formation.

[0008] Methods for solving problems

[0009] According to one aspect of the present invention, a technique is provided that includes a film-forming process comprising performing (a) and (b) below, and preferentially forming a film containing a metal element on a first surface compared to a second surface.

[0010] (a): A process of (a1) supplying a first gas containing the metal element to a substrate and (a2) supplying a second gas containing the metal element to the substrate, thereby forming a metal-containing substance containing the metal element on at least a portion of the substrate, wherein the substrate is a substrate having a first surface as the surface of the first substance and a second surface as the surface of a second substance different from the first substance;

[0011] (b): The process of supplying reactive gases to the substrate.

[0012] Wherein, (a) includes the period Tc during which (a1) and (a2) are performed at least partially simultaneously.

[0013] The first gas etches the metal-containing material at a first rate.

[0014] The second gas etches the metal-containing material at a second rate that is higher than the first rate.

[0015] The effects of the invention

[0016] According to the present invention, selective film formation can be performed efficiently. Attached Figure Description

[0017] Figure 1 This is a schematic longitudinal cross-sectional view of a vertical processing furnace in a substrate processing apparatus according to one aspect of the present invention.

[0018] Figure 2 This is a schematic configuration diagram of the controller of a substrate processing apparatus according to one aspect of the present invention, and is a block diagram showing the control system of the controller.

[0019] Figure 3 This is a diagram illustrating a film-forming process in one embodiment of the present invention.

[0020] Figure 4 (A) in the figure is a diagram showing a substrate with a recess; Figure 4 (B) in the figure shows the formation of a film in a recess on a substrate; Figure 4 (C) in the figure shows a case where a film is formed on a substrate to embed the recess.

[0021] Figure 5 (A) in the figure is a modified example of the film-forming process in one aspect of the present invention; Figure 5 Figure (B) is a modified example of the film-forming process in one aspect of the present invention.

[0022] Figure 6 This is a diagram illustrating a modified example of the film-forming process in one aspect of the present invention.

[0023] Explanation of reference numerals in the attached figures

[0024] 200 wafers (substrates) Detailed Implementation

[0025] The following is mainly based on Figures 1-4 One aspect of the present invention will be described below. It should be noted that the drawings used in the following description are schematic, and the dimensional relationships and ratios of the elements shown in the drawings may not necessarily correspond to reality. Furthermore, the dimensional relationships and ratios of the elements may not be consistent between different drawings.

[0026] (1) Composition of substrate processing device

[0027] like Figure 1 As shown, the processing furnace 202 has a heater 207 as a heating system (temperature control unit). The heater 207 also serves as an activation mechanism (activation unit) for activating (exciting) gases by heat.

[0028] A reaction tube 203 is disposed inside the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and is formed into a cylindrical shape that is closed at the top and open at the bottom. A manifold 209 supporting the reaction tube 203 is disposed below the reaction tube 203. An O-ring 220a as a sealing component is provided between the manifold 209 and the reaction tube 203. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 capable of accommodating one or more wafers 200 as substrates is formed inside the processing container.

[0029] Inside the processing chamber 201, nozzles 249a and 249b are arranged to penetrate the side wall of the manifold 209. Gas supply pipes (pipelines) 232a and 232b are respectively connected to nozzles 249a and 249b.

[0030] On gas supply pipes 232a and 232b, mass flow controllers (MFCs) 241a and 241b, serving as flow controllers (flow control units), and valves 243a and 243b, serving as on / off valves, are sequentially installed from the upstream side. Gas supply pipes 232c and 232e are connected downstream of valve 243a on gas supply pipe 232a. Gas supply pipe 232d is connected downstream of valve 243b on gas supply pipe 232b. On gas supply pipes 232c, 232d, and 232e, MFCs 241c, 241d, and 241e, and valves 243c, 243d, and 243e, are sequentially installed from the upstream side.

[0031] Nozzles 249a and 249b are respectively arranged in a ring-shaped space between the inner wall of the reaction tube 203 and the wafer 200 when viewed from above, and are positioned vertically upwards along the inner wall of the reaction tube 203 from bottom to top and towards the loading direction of the wafer 200. Gas supply holes 250a and 250b are respectively provided on the sides of nozzles 249a and 249b for supplying gas. Gas supply holes 250a and 250b open towards the center of the reaction tube 203, and can supply gas towards the wafer 200. Multiple gas supply holes 250a and 250b are provided from the bottom to the top of the reaction tube 203.

[0032] A first gas containing metal element X is supplied as a raw material gas into the processing chamber 201 through gas supply pipe 232a via MFC 241a, valve 243a, and nozzle 249a.

[0033] A second gas containing metal element X is supplied as a raw material gas into the processing chamber 201 through gas supply pipe 232c via MFC241c, valve 243c, and nozzle 249a.

[0034] The reaction gas that reacts with the raw material gas is supplied from the gas supply pipe 232b through MFC 241b, valve 243b, and nozzle 249b into the processing chamber 201.

[0035] Inactive gases are supplied to the processing chamber 201 from gas supply pipes 232d and 232e via MFCs 241d and 241e, valves 243d and 243e, gas supply pipes 232b and 232a, and nozzles 249b and 249a, respectively.

[0036] The first gas supply system mainly consists of gas supply pipe 232a, MFC 241a, and valve 243a. The second gas supply system mainly consists of gas supply pipe 232c, MFC 241c, and valve 243c. The first and second gas supply systems can also be collectively referred to as the raw material gas supply system or the metal-containing gas supply system containing metal element X. The reaction gas supply system mainly consists of gas supply pipe 232b, MFC 241b, and valve 243b. The first, second, and reaction gas supply systems can also be collectively referred to as the gas supply system. The inactive gas supply system mainly consists of gas supply pipes 232d and 232e, MFC 241d and 241e, and valves 243d and 243e. The inactive gas supply system can also be included within the gas supply system.

[0037] Any or all of the aforementioned supply systems can also be configured as an integrated supply system 248, which integrates valves 243a-243e, MFCs 241a-241e, etc. The integrated supply system 248 is configured to be connected to gas supply pipes 232a-232e respectively, and the supply operation of various gases to the gas supply pipes 232a-232e is controlled by the controller 121 described later, namely the opening and closing operation of valves 243a-243e, the flow regulation operation based on MFCs 241a-241e, etc.

[0038] An exhaust pipe 231 for venting the atmosphere inside the processing chamber 201 is provided on the reaction tube 203. A vacuum pump 246, serving as a vacuum venting device, is connected to the exhaust pipe 231 via a pressure sensor 245 (a pressure detector, or pressure detection unit) and an APC (Auto Pressure Controller) valve 244 (a pressure regulator, or pressure regulating unit). The APC valve 244 is configured to allow for vacuum venting and cessation of vacuum venting within the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating. Furthermore, while the vacuum pump 246 is operating, the pressure inside the processing chamber 201 can be adjusted by regulating the valve opening based on the pressure information detected by the pressure sensor 245. The exhaust system mainly consists of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may also be included in the exhaust system.

[0039] A sealing cover 219, serving as a furnace opening cover, is provided below the manifold 209 to airtightly seal the lower opening of the manifold 209. An O-ring 220b, serving as a sealing component, is provided on the upper surface of the sealing cover 219, abutting against the lower end of the manifold 209. A rotation mechanism 267, described later, is provided below the sealing cover 219 to rotate the crystal boat 217. The rotation shaft 255 of the rotation mechanism 267 passes through the sealing cover 219 and is connected to the crystal boat 217. The crystal boat lift 115 is configured to move the crystal boat 217 in and out of the processing chamber 201 by raising and lowering the sealing cover 219. The crystal boat lift 115 is configured as a conveying device (conveyor) for conveying the crystal boat 217, i.e., the wafer 200, in and out of the processing chamber 201.

[0040] The crystal boat 217, serving as a substrate support, is configured to support multiple wafers 200, for example, 25 to 200 wafers 200 arranged horizontally and aligned centrally along a vertical direction in a multi-layered manner, with the wafers spaced apart. The crystal boat 217 is made of heat-resistant materials such as quartz or SiC. A heat-insulating plate 218, also made of heat-resistant materials such as quartz or SiC, is supported in multiple layers at the bottom of the crystal boat 217. It should be noted that the numerical range "25 to 200 wafers" in this specification refers to the inclusion of both the lower and upper limits within that range. Therefore, for example, "25 to 200 wafers" means "more than 25 wafers and less than 200 wafers." The same applies to other numerical ranges.

[0041] A temperature sensor 263, serving as a temperature detector, is installed inside the reaction tube 203. By adjusting the energization of the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature within the processing chamber 201 is adjusted to achieve the desired temperature distribution. The temperature sensor 263 is configured in an L-shape and is installed along the inner wall of the reaction tube 203.

[0042] like Figure 2 As shown, the controller 121, serving as the control unit (control unit), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, storage device 121c, and I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, such as a touch panel, is connected to the controller 121. Furthermore, the substrate processing apparatus can be configured to have one control unit or multiple control units. That is, one control unit can be used to control the processing sequence described later, or multiple control units can be used to control the processing sequence described later. Additionally, multiple control units can be configured as a control system interconnected via a wired or wireless communication network, or the control system as a whole can control the processing sequence described later. When the term "control unit" is used in this specification, in addition to the case of having one control unit, there are also cases of having multiple control units or a control system composed of multiple control units.

[0043] The storage device 121c is configured such as flash memory or HDD (Hard Disk Drive). The storage device 121c stores, in a readable manner, a control program that controls the operation of the substrate processing apparatus 100, and a process flow that describes the substrate processing steps and conditions, as described later. The process flow is a combination of steps in the substrate processing described later, executed by the controller 121 in a manner that yields a predetermined result, and functions as a program (or program article). Hereinafter, the process flow, control program, etc., will be collectively referred to as a program (or program article). Furthermore, the process flow will be simply referred to as a process. When the term "program" is used in this specification, there may be cases where only the process flow is included, cases where only the control program is included, or cases where both are included. The RAM 121b is configured as a memory area (working area) that temporarily holds programs, data, etc., read from the CPU 121a.

[0044] I / O port 121d is connected to the aforementioned MFC241a~241e, valves 243a~243e, pressure sensor 245, APC valve 244, vacuum pump 246, heater 207, temperature sensor 263, rotating mechanism 267, crystal boat lift 115, etc.

[0045] CPU 121a is configured to read and execute control programs from storage device 121c, and to read processes from storage device 121c based on inputs such as operation commands from input / output device 122. CPU 121a is configured to control the following according to the read processes: flow regulation of various gases based on MFCs 241a to 241e, opening and closing of valves 243a to 243e, opening and closing of APC valve 244 and pressure regulation of APC valve 244 based on pressure sensor 245, starting and stopping of vacuum pump 246, temperature regulation of heater 207 based on temperature sensor 263, rotation and rotation speed regulation of crystal boat 217 based on rotation mechanism 267, and lifting of crystal boat 217 based on crystal boat lift 115.

[0046] The controller 121 can be configured by installing the aforementioned program stored in an external storage device (such as a hard disk, a CD, or a semiconductor memory such as a USB flash drive) 123 into a computer. The storage device 121c and the external storage device 123 constitute a computer-readable recording medium containing a program. Hereinafter, they will be collectively referred to as a recording medium. When the term "recording medium" is used in this specification, there may be a case where only the storage device 121c is included, a case where only the external storage device 123 is included, or a case where both are included. It should be noted that the external storage device 123 may also be omitted, and the program may be provided to the computer using a communication unit such as the Internet or a dedicated line.

[0047] (2) Substrate processing process

[0048] use Figure 3 and Figure 4 The following example illustrates a process sequence in which a film 500 containing a metal element X is formed on the first surface 300 of a wafer 200 having a first surface 300 as a first material and a second surface 400 as a second material, as part of a substrate processing step in the manufacturing process of a semiconductor device, using the substrate processing apparatus 100 described above. In the following description, the operation of each component constituting the substrate processing apparatus 100 is controlled by the controller 121.

[0049] like Figure 4As shown in (A), a recess 350 is formed on the surface of wafer 200, and a first surface 300 is formed on the bottom of the recess 350 and a second surface 400 is formed on the sidewalls. In the following substrate processing steps, a film 500 containing metal element X embedded in the recess 350 is selectively formed on the first surface 300 within the recess 350. That is, in this embodiment, a film 500 containing metal element X is preferentially (also referred to as selectively) formed on the first surface 300 within the recess 350 of wafer 200 having a first surface 300 and a second surface 400, compared to the second surface 400. Here, in this specification, the phrase "preferentially (selectively) formed on the first surface 300 compared to the second surface 400" includes not only the case where no film is formed on the second surface 400, but also the case where a film relatively thinner than the film formed on the first surface 300 is formed on the second surface 400.

[0050] Here, the first substance and the second substance are different substances. Specifically, the first substance is a film with high conductivity, constructed using a conductive material, i.e., a conductive film. The first surface 300 of the first substance is, for example, a molybdenum (Mo) film, a titanium nitride (TiN) film, etc. The second surface 400 of the second substance is constructed using a non-conductive material and is a film with lower conductivity than the first surface 300. The second surface 400 is, for example, an oxide film such as silicon oxide (SiO) film, a semiconductor film, etc.

[0051] Regarding the use of the term "wafer" in this specification, it may refer to the wafer itself, or to a laminate of the wafer and a specified layer or film formed on its surface. Regarding the use of the term "surface of the wafer" in this specification, it may refer to the surface of the wafer itself, or to the surface of a specified layer, etc., formed on the wafer. In this specification, when it is described as "forming a specified layer on the wafer," it may refer to forming the specified layer directly on the surface of the wafer itself, or to forming the specified layer on a layer, etc., formed on the wafer. In this specification, the use of "substrate" is also synonymous with the use of "wafer."

[0052] (Chip loading)

[0053] When multiple wafers 200 are loaded (wafer filling) into the crystal boat 217, such as Figure 1 As shown, a crystal boat 217 supporting multiple wafers 200 is lifted by a crystal boat elevator 115 and loaded into (crystal boat loading) the processing chamber 201, where it is housed in a processing container. In this state, the sealing cap 219 closes the lower opening of the manifold 209 via an O-ring 220b.

[0054] (Pressure and temperature regulation)

[0055] Vacuum pump 246 is used to exhaust vacuum, so that the space inside processing chamber 201, i.e., where wafer 200 is located, reaches the desired pressure (vacuum level). At this time, the pressure inside processing chamber 201 is measured by pressure sensor 245, and based on this measured pressure information, APC valve 244 is controlled by feedback (pressure regulation). Vacuum pump 246 remains continuously operating at least until the processing of wafer 200 is completed. Additionally, heating is performed by heater 207 to achieve the desired temperature inside processing chamber 201. At this time, the electrical current supplied to heater 207 is controlled by feedback (temperature regulation) based on temperature information detected by temperature sensor 263 to achieve the desired temperature distribution inside processing chamber 201. Heating inside processing chamber 201 based on heater 207 continues at least until the processing of wafer 200 is completed.

[0056] (Film forming process)

[0057] In the film-forming process, steps S11 to S14 are performed a specified number of times.

[0058] (Raw material gas supply, step S11)

[0059] ((First gas supply, step S111))

[0060] First, a first gas containing metal element X is supplied to the wafer 200 within the processing chamber 201. Specifically, valve 243a is opened, allowing the first gas to flow into gas supply pipe 232a. The first gas, with flow rate regulated by MFC 241a, is supplied into the processing chamber 201 via nozzle 249a and exhausted from exhaust pipe 231. Simultaneously, valve 243e is opened, allowing an inactive gas to flow into gas supply pipe 232e. The inactive gas, with flow rate regulated by MFC 241e, is supplied into the processing chamber 201 along with the first gas and exhausted from exhaust pipe 231. Furthermore, to prevent the first gas from entering nozzle 249b, valve 243d is opened, allowing the inactive gas to flow into gas supply pipe 232d. The inactive gas is supplied into the processing chamber 201 via gas supply pipe 232d and nozzle 249b and exhausted from exhaust pipe 231. At this time, the primary gas flowing within the processing chamber 201 is the first gas.

[0061] As a processing condition in step S111, an example can be given:

[0062] Supply time of the first gas (period T1): 0.01–60 seconds, preferably 2–20 seconds; Processing pressure: 10–13300 Pa, preferably 20–1330 Pa.

[0063] The supply flow rate of the first gas is 0.01–1 slm, preferably 0.2–0.9 slm.

[0064] The supply flow rate of the inactive gas is 0.02 to 2 slm, preferably 0.4 to 1.8 slm.

[0065] It should be noted that the processing temperature is preferably set to substantially the same temperature in any of the following steps. Furthermore, the processing temperature in this specification refers to the temperature of the wafer 200 or the temperature inside the processing chamber 201, and the processing pressure refers to the pressure inside the processing chamber 201. Additionally, the processing time refers to the duration of the processing. These also apply to the following description.

[0066] By supplying the first gas, a metallic substance Y containing a metal element X is formed on at least a portion of the wafer 200. Here, the metallic substance Y is at least one of the following: molecules of the first or second gas chemically or physically adsorbed onto the surface of the wafer 200; a substance containing a metal element X as part of the molecular structure of the first or second gas; a compound containing a metal element X chemically bonded to other elements; or a reduced elemental form of the metal element X. Specifically, for example, the metallic substance Y may be molecules of a Mo-containing gas, part of the molecular structure of a Mo-containing gas, Mo, etc.

[0067] Here, the first gas forms a metallic substance Y on the wafer 200. Furthermore, the first gas has the property of etching (also called removing) the metallic substance Y on the wafer 200 at a first rate lower than the etching rate of the second gas described later. It should be noted that the first gas preferably forms the metallic substance Y on the wafer 200 at a film-forming rate higher than that of the second gas. That is, it can also be said that the first gas is a gas that easily forms a film of the metallic substance Y on the wafer 200 and is not easily removed from the wafer 200. In this step, by supplying the first gas, the metallic substance Y is formed at a high film-forming rate while the metallic substance Y formed on the wafer 200 is etched (removed) at an etching rate lower than that of the second gas.

[0068] As the first gas and the second gas described later, a gas used to form a metallic substance Y on the wafer 200 and then etch the metallic substance Y on the wafer 200 can be used. For example, a gas containing a metallic element X and a halogen element can be used as such a gas. Alternatively, as the first gas and the second gas described later, a gas containing a metallic element X, a halogen element, and oxygen (O) can be used; or a gas containing a metallic element X and a halogen element but without O. A gas containing a metallic element X, a halogen element, and O may sometimes be less effective at etching the metallic substance Y compared to a gas without O.

[0069] Metal element X can be, for example, metal elements from periods 4 to 6 and groups 3 to 14. Preferably, a transition metal element can be used as metal element X. In this case, the effects of this method are more easily obtained. More preferably, a transition metal element from period 5 can be used as metal element X. In this case, the effects of this method are more easily obtained. For example, Mo can be used as a transition metal element from period 5. In this case, the effects of this method are particularly easy to obtain.

[0070] Examples of halogen elements that can be used include chlorine (Cl), fluorine (F), bromine (Br), and iodine (I). One or more of these elements can be used as halogen elements.

[0071] Specifically, as the first gas, a gas containing Mo, Cl, and O can be used, for example. As the gas containing Mo, Cl, and O, a gas containing any one of molybdenum dioxide (MoO2Cl2) gas, molybdenum tetrachloride (MoOCl4) gas, or a gas containing one or more of them can be used.

[0072] Furthermore, when using a gas containing a transition metal element from the 5th period with electron orbitals similar to Mo, and Cl and O as the first gas, it is easy to obtain the same effect as when using a gas containing Mo, Cl, and O. Examples of transition metal elements from the 5th period that can be used include yttrium (Y), zirconium (Zr), niobium (Nb), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and cadmium (Cd).

[0073] As inert gases, in addition to nitrogen (N2), rare gases such as argon (Ar), helium (He), neon (Ne), and xenon (Xe) can also be used. More than one of these gases can be used as an inert gas.

[0074] ((Simultaneous supply of the first gas and the second gas, step S112))

[0075] Following step S111, while the first gas is continuously supplied, the supply of a second gas containing the metal element X begins. That is, the supply of the second gas begins immediately after the supply of the first gas. Specifically, while the first gas is continuously supplied, valve 243c is opened, allowing both the first and second gases to flow simultaneously in gas supply pipe 232a. The second gas, with flow regulation using MFC 241c, is supplied to the processing chamber 201 along with the first gas and exhausted from exhaust pipe 231. Simultaneously, valve 243e is opened, allowing inactive gas to flow into gas supply pipe 232e. The inactive gas, with flow regulation using MFC 241e, is supplied to the processing chamber 201 along with the first and second gases and exhausted from exhaust pipe 231. Furthermore, to prevent the first and second gases from entering nozzle 249b, valve 243d is opened, allowing inactive gas to flow into gas supply pipe 232d. Inactive gas is supplied into the processing chamber 201 via gas supply pipe 232d and nozzle 249b, and exhausted from exhaust pipe 231. At this time, the main gases flowing in the processing chamber 201 are the first gas and the second gas.

[0076] As a processing condition in step S112, an example can be given:

[0077] The simultaneous supply time (period Tc) of the first and second gases: 0.01 to 60 seconds, preferably 2 to 40 seconds.

[0078] Processing pressure: 10–13300 Pa, preferably 20–1330 Pa

[0079] The supply flow rate of the first gas is 0.001–1 slm, preferably 0.2–0.9 slm.

[0080] The supply flow rate of the second gas is 0.1–10 sccm, preferably 1–5 sccm.

[0081] The supply flow rate of the inactive gas is 0.1 to 20 slm, preferably 1 to 10 slm.

[0082] By simultaneously supplying the first gas and the second gas, at least a portion of the wafer 200 is formed with a metallic substance Y containing the metallic element X.

[0083] Here, the second gas forms a metallic substance Y on the wafer 200. Furthermore, it has the property of etching (also called removing) the metallic substance Y on the wafer 200 at a second rate higher than the etching rate of the first gas (i.e., the first rate). It should be noted that the second gas preferably forms the metallic substance Y on the wafer 200 at a film-forming rate lower than that of the first gas. That is, the second gas can also be described as a gas that does not easily form a metallic substance Y on the wafer 200 but easily removes the metallic substance Y from the wafer 200.

[0084] As the second gas, for example, a gas containing the aforementioned metallic element X and the aforementioned halogen element, but without oxygen, can be used. The second gas can also be a gas composed of metallic element X and a halogen element. In such cases, the etching rate of the second gas is more easily increased compared to the first gas, thus making it easier to obtain the effects of this method. It should be noted that, as the second gas, a gas containing metallic element X, a halogen element, and oxygen can also be used.

[0085] Specifically, as the second gas, a gas containing Mo and Cl can be used, for example. As the gas containing Mo and Cl, a gas containing any one of molybdenum pentachloride (MoCl5) gas, molybdenum tetrachloride (MoCl4) gas, or a gas containing one or more of them can be used.

[0086] Here, the first gas etches the metallic material Y at a lower rate than the second gas. Therefore, when forming a film on the wafer 200 using only the first gas, the film formation rate can be improved compared to using only the second gas. However, due to the low etching rate, the metallic material Y on the second surface 400 other than the first surface 300 becomes difficult to remove, thus reducing selectivity.

[0087] On the other hand, the second gas etches the metallic substance Y at a higher rate than the first gas. Therefore, when film deposition is performed on the wafer 200 using only the second gas, the metallic substance Y on the second surface 400 is easily removed, thus improving selectivity. However, the second gas can sometimes damage the surface of the wafer 200 due to etching. Furthermore, in order to suppress etching caused by the second gas, for example, if the exposure of the second gas to the wafer 200 is reduced by supplying more of other gases (e.g., inactive gases), the film deposition rate on the first surface 300 also decreases.

[0088] Here, damage to the wafer 200 refers to, for example, the removal or modification of the surface of the wafer 200 (e.g., one or more of the substances formed on the wafer 200, such as the substance that mainly constitutes the wafer 200, the first substance constituting the first surface 300, the second substance constituting the second surface 400, etc.).

[0089] In step S112, the period for supplying the first gas and the period for supplying the second gas are repeated. That is, step S11 has a period Tc during which the supply of the first gas and the supply of the second gas are partially simultaneous. During this period Tc, the second gas is supplied to the wafer 200 based on the first gas. Therefore, the exposure of the wafer 200 to the second gas is reduced. Thus, damage to the wafer 200 caused by the high etching rate of the second gas can be reduced.

[0090] Furthermore, prior to this step, a period T1 is provided where only the first gas is supplied. That is, after the first gas is supplied to the wafer 200, the second gas is supplied. In this case, when the second gas supply of this step begins, at least a portion of the wafer 200 has already been formed with the first gas containing a metallic substance Y. Therefore, damage to the wafer 200 can be suppressed.

[0091] Furthermore, the first gas also has the property of forming a metallic substance Y on the wafer 200, so the film formation rate is less likely to decrease in this step. Therefore, selectivity can be improved while suppressing the decrease in film formation rate and damage to the wafer 200. Thus, selective film formation can be performed efficiently.

[0092] Here, "exposure amount of the second gas" is calculated, for example, as "the value obtained by integrating the partial pressure of the second gas in the space where the wafer 200 exists during the process of supplying the second gas using the time from the start to the end of the supply of the second gas (hereinafter referred to as "supply time of the second gas"). Alternatively, "partial pressure of the second gas" is calculated, for example, as "the value obtained by integrating the product of the mole fraction of the second gas and the processing pressure in the space where the wafer 200 exists over time." The same applies to other gases.

[0093] ((Second gas supply, step S113))

[0094] After step S112, the supply of the first gas is stopped while the supply of the second gas continues. That is, the supply of the second gas ends after the supply of the first gas ends. Specifically, valve 243a is closed, so that only the second gas flows into the gas supply pipe 232a, and the first gas does not flow into it. The second gas is supplied to the processing chamber 201 with flow regulation using MFC 241c and is exhausted from the exhaust pipe 231. At the same time, valve 243e is opened, allowing inactive gas to flow into the gas supply pipe 232e. The inactive gas is supplied to the processing chamber 201 together with the second gas with flow regulation using MFC 241e and is exhausted from the exhaust pipe 231. In addition, to prevent the second gas from entering the nozzle 249b, valve 243d is opened, allowing inactive gas to flow into the gas supply pipe 232d. The inactive gas is supplied to the processing chamber 201 via the gas supply pipe 232d and the nozzle 249b and is exhausted from the exhaust pipe 231. At this time, the main gas flowing in the processing chamber 201 is the second gas.

[0095] As a processing condition in step S113, an example can be given:

[0096] Supply time of the second gas (period T2): 0.01–60 seconds, preferably 2–20 seconds; Processing pressure: 10–13300 Pa, preferably 20–1330 Pa.

[0097] The supply flow rate of the second gas is 0.1–10 sccm, preferably 1–5 sccm.

[0098] The supply flow rate of the inactive gas is 0.1 to 20 slm, preferably 1 to 10 slm.

[0099] By supplying the second gas, a metallic substance Y containing metal element X is formed on at least a portion of the wafer 200. By supplying the second gas with a high etching rate, the metallic substance Y on the second surface 400 is easily removed. Therefore, the metallic substance Y containing metal element X is preferentially formed on the first surface 300 of the wafer 200 compared to the second surface 400.

[0100] Thus, after the period Tc in step S112 where both the first gas and the second gas are supplied simultaneously, a period T2 is set where only the second gas is supplied. This allows the removal of the metallic substance Y formed on the second surface 400 during period Tc. In other words, since the metallic substance Y is also formed on the second surface 400 during period Tc, damage to the wafer 200 can be suppressed even when the second gas, which has a high etching rate, is supplied.

[0101] Furthermore, when forming the film 500 containing the metal substance Y by embedding it in the recess 350, the opening side and the bottom side of the recess 350 (i.e., on the first surface 300) are more easily etched. Therefore, the metal substance Y formed on the sidewall of the recess 350, i.e., the second surface 400, during period Tc is removed by using a second gas with a low film formation rate and a high etching rate. Therefore, the metal substance Y is less likely to form on the second surface 400, which serves as the sidewall of the recess 350, and the formation of pores and seams in the film 500 embedded in the recess 350 can be suppressed. In other words, it is possible to remove the metal substance Y formed on the second surface 400 within the recess 350 while promoting the formation of the metal substance Y on the bottom side of the recess 350, thus achieving both film formation rate and selectivity.

[0102] (Purge, step S12)

[0103] After a metallic substance Y containing metallic element X is formed on at least a portion of the wafer 200, with valves 243a-243c closed, valves 243d and 243e are opened, and an inactive gas is supplied as purging gas to gas supply pipes 232a and 232b via gas supply pipes 232d and 232e. Meanwhile, with the APC valve 244 of the exhaust pipe 231 remaining open, a vacuum pump 246 is used to purge the processing chamber 201. At this time, any residual gas and reaction byproducts in the processing chamber 201 are removed.

[0104] (Reaction gas supply, step S13)

[0105] Next, reactive gas is supplied to the wafer 200 within the processing chamber 201. Specifically, valve 243b is opened, allowing reactive gas to flow into gas supply pipe 232b. The reactive gas, with flow rate regulated by MFC 241b, is supplied into the processing chamber 201 via nozzle 249b and exhausted from exhaust pipe 231. Simultaneously, valve 243d is opened, allowing inactive gas to flow into gas supply pipe 232d. The inactive gas, with flow rate regulated by MFC 241d, is supplied into the processing chamber 201 along with the reactive gas and exhausted from exhaust pipe 231. Furthermore, to prevent reactive gas from entering nozzle 249a, valve 243e is opened, allowing inactive gas to flow into gas supply pipe 232e. The inactive gas is supplied into the processing chamber 201 via gas supply pipe 232e and nozzle 249a and exhausted from exhaust pipe 231. At this time, the main gas flowing within the processing chamber 201 is reactive gas.

[0106] As a processing condition in step S13, an example can be given:

[0107] The supply time of the reactant gas is 0.01 to 600 seconds, preferably 10 to 300 seconds.

[0108] Processing pressure: 10–26600 Pa, preferably 100–13300 Pa

[0109] The supply flow rate of the reactant gas is 0.1–50 slm, preferably 10–40 slm.

[0110] The supply flow rate of the inactive gas is 0.1–5 slm, preferably 1–3 slm.

[0111] By supplying the reaction gas, the halogens contained in the first and second gases are reduced by the reaction gas, such as... Figure 4 As shown in (B), a layer containing metal element X is formed on at least a portion of the wafer 200, i.e., on the first surface 300 on which metal-containing material Y containing metal element X is formed, with preference to the second surface 400.

[0112] As reactant gases, for example, gases that react with and reduce the first and second gases can be used. Examples of reactant gases include hydrogen (H2), deuterium (D2), borane (BH3), diborane (B2H6), carbon monoxide (CO), ammonia (NH3), silane (SiH4), disilane (Si2H6), propane (Si3H8), germanane (GeH4), and digerane (Ge2H6).

[0113] In addition to reducing gases, gases that react with metallic substance Y to form conductive substances, such as nitriding gases, sulfiding gases, selenizing gases, and tellurizing gases, can also be used as reacting gases. For example, when the first reacting gas is any one of nitriding gas, sulfiding gas, selenizing gas, or tellurizing gas, nitriding films, sulfiding films, selenizing films, or tellurizing films can be formed on the wafer.

[0114] As a nitriding gas, one or more of the following hydrogen nitriding gases can be used: NH3 gas, diazoxide (N2H2) gas, hydrazine (N2H4) gas, etc. As a sulfiding gas, gases including thioalkylene (H2S), dithionane (H2S2), diammonium sulfide ((NH4)2S), dimethyl sulfide ((CH3)2S), etc., can be used. As a sulfiding gas, one or more of these gases can be used. As a selenizing gas, gases including hydrogen selenide (H2Se), diselenoylene (H2Se2), dimethylselenide ((CH3)2Se), etc., can be used. As a selenizing gas, one or more of these gases can be used. As a tellurizing gas, gases including hydrogen telluride (H2Te), dihydrogen telluride (H2Te2), dimethyl telluride ((CH3)2Te), etc., can be used. As a tellurizing gas, one or more of these gases can be used.

[0115] (Purge, step S14)

[0116] Next, an inactive gas is supplied as a purge gas through the same processing steps as in step S12 described above, and the APC valve 244 of the exhaust pipe 231 is kept open, and the processing chamber 201 is purged by vacuum exhaust through the vacuum pump 246. At this time, the gas and reaction byproducts remaining in the processing chamber 201 are removed.

[0117] (Number of times specified)

[0118] The above steps S11 to S14 will be repeated a specified number of times (n times, where n is an integer of 1 or 2 or higher). Thus, as... Figure 4 As shown in (C), a film 500 containing the metal element X of a predetermined thickness is preferentially formed in the recess 350 on the wafer 200 and on the first surface 300 of the wafer 200 having a first surface 300 and a second surface 400, compared with the second surface 400.

[0119] At temperatures below 200°C, substances formed by the solidification of raw material gases can sometimes easily form within the processing chamber 201. Furthermore, at temperatures above 650°C, the resistivity of the film 500 can sometimes increase due to cohesion. Therefore, by performing the film-forming process at a temperature between 200°C and 650°C, it is possible to easily form a low-resistivity film while suppressing the formation of foreign matter. Additionally, by performing the film-forming process at a temperature between 300°C and 600°C, it is possible to easily form a film with even lower resistivity while further suppressing the formation of foreign matter. Furthermore, by performing the film-forming process at a temperature between 350°C and 550°C, it is possible to easily form a film with extremely low resistivity while significantly suppressing the formation of foreign matter.

[0120] Furthermore, when performing the film deposition process at temperatures below 400°C, it becomes less effective to form the metallic substance Y based on the raw material gas compared to temperatures above 400°C. On the other hand, the ease with which the raw material gas etches the metallic substance Y is less likely to change significantly compared to temperatures above 400°C. Therefore, when performing the film deposition process on the wafer 200 using only raw material gases that exhibit high etchability at temperatures below 400°C, damage to the wafer 200 is more likely to increase during the sufficient film deposition period. As with the technology of the present invention, by simultaneously supplying multiple raw material gases with different etchability during the period Tc, even when performing the film deposition process at temperatures below 400°C, it is possible to selectively and effectively deposit the film while suppressing damage to the wafer 200.

[0121] The film 500 containing metal element X is a film made of a conductive material. For example, a metal-containing film containing metal element X can be formed as a film made of a conductive material. For example, a Mo-containing film can be formed as a metal-containing film.

[0122] (Post-purging and atmospheric pressure recovery)

[0123] Inert gases are supplied into the processing chamber 201 through gas supply pipes 232d and 232e, respectively, and exhaust gases are discharged through exhaust pipe 231. The inert gases serve as purge gases. As a result, the processing chamber 201 is purged, and residual gases and reaction byproducts within it are removed (post-purging). Then, the atmosphere within the processing chamber 201 is replaced with the inert gases (inert gas replacement), and the pressure within the processing chamber 201 is restored to atmospheric pressure (atmospheric pressure restoration).

[0124] (Chip removal)

[0125] The sealing cover 219 is lowered by the crystal boat lift 115, opening the lower end of the manifold 209. Then, the processed wafer 200, supported by the crystal boat 217, is moved from the lower end of the manifold 209 to the outside of the reaction tube 203 (crystal boat unloading). The processed wafer 200 is then removed from the crystal boat 217 (wafer removal).

[0126] (3) Other methods

[0127] Next, a modified example of the film-forming process in the above method will be described in detail. In the following modified examples, only the differences from the above method will be described in detail. Figure 5 (A) and Figure 5 In (B) above, the timing of the first gas supply and the second gas supply in the raw material gas supply step (S11) of the film forming process is different.

[0128] (Variation Example 1)

[0129] In this variation, such as Figure 5 As shown in (A), in one cycle of the film-forming process, the supply of the first gas and the supply of the second gas start and end simultaneously. That is, in this modified example, there is a period Tc during which the first gas and the second gas are supplied simultaneously in one cycle of the film-forming process.

[0130] In this modified example, at least some of the effects described above can be achieved. For example, selectivity can be improved while suppressing the decrease in film deposition rate and damage to the wafer 200. Therefore, selective film deposition can be performed efficiently. In addition, in this modified example, processing time can be further shortened, and productivity can be improved.

[0131] (Variation Example 2)

[0132] In this variation, such as Figure 5 As shown in (B), in one cycle of the film-forming process, the supply of the second gas begins before the supply of the first gas and ends after the supply of the first gas ends. In other words, the supply of the first gas begins and ends during the supply of the second gas. That is, in this modified example, in one cycle of the film-forming process, there is a period Tc (step S115) during which the first gas and the second gas are supplied simultaneously, a period T3 (step S114) before period Tc (step S115) during which only the second gas is supplied, and a period T4 (step S116) after period Tc (step S115) during which only the second gas is supplied.

[0133] In this modified example, at least some of the effects described above can also be obtained. That is, selectivity can be improved while suppressing the decrease in film formation rate and damage to the wafer 200. Therefore, selective film formation can be performed efficiently. In addition, in this modified example, by supplying a second gas with a high etching rate before the supply of the first gas begins, the first gas can be supplied in a state where metal-containing substances Y are less likely to exist on the second surface 400. Therefore, the further growth of undesirable metal-containing substances Y, etc., formed on the second surface 400 can be suppressed, and thus selectivity can be further improved.

[0134] Alternatively, in one cycle of the film-forming process, the supply of the second gas can begin before the supply of the first gas starts and end before the supply of the first gas ends. In this case, at least some of the effects of the methods described above can be obtained.

[0135] (Variation Example 3)

[0136] In this variation, such as Figure 6 As shown, a second film-forming process is performed after the first film-forming process. In the first film-forming process, the steps S21 (simultaneously supplying a% of the first gas and (100-a)% of the second gas), S22 (similar to step S12), S23 (similar to step S13), and S24 (similar to step S14) are performed a predetermined number of times (n times, where n is an integer of 1 or 2 or higher). In the second film-forming process, the steps S31 (simultaneously supplying b% of the first gas and (100-b)% of the second gas), S32 (similar to step 12), S33 (similar to step 13), and S34 (similar to step S14) are performed a predetermined number of times (m times, where m is an integer of 1 or 2 or higher). Here, a and b are integers from 0 to 100, and a and b are distinct numbers.

[0137] Here, in steps S21 and S31, the proportions of the amounts of the first gas and the second gas supplied to the wafer 200 relative to the total amount of the first gas (e.g., flow rate, number of molecules, and exposure per unit time) and the second gas are set as a% and b%, respectively. a and b are integers from 0 to 100. Here, when a or b is 0, it means that the first gas is not supplied in the first or second film-forming process. Similarly, when a or b is 100, it means that the second gas is not supplied in the first or second film-forming process. These conditions are also the same in the following description. In the following description, the first film-forming process when a is 100 is designated as the third film-forming process, and the second film-forming process when b is 100 is designated as the fourth film-forming process.

[0138] It should be noted that the above-described methods and variations of Example 2 can be combined for each of the first, second, and fourth film-forming processes. For example, the supply of either the first gas or the second gas can be performed before at least one of steps S21 and S31, as in steps S111 and S114. Alternatively, the supply of only the second gas can be performed before at least one of steps S21 and S31, as in steps S113 and S116. Furthermore, the supply of only the first gas can be performed after at least one of steps S21 and S31. That is, in the first, second, and fourth film-forming processes, the supply of the first gas and the supply of the second gas to the wafer 200 can be performed at least partially simultaneously during a certain period Tc'. In this case, at least some of the effects described above can be obtained.

[0139] Preferably, the second or fourth film deposition process is performed on the wafer 200 under conditions where the metal-containing substance Y can be removed more easily than in the first or third film deposition process. In this case, the metal-containing substance Y on the wafer 200 is not easily removed in the first or third film deposition process, thus the film deposition rate can be increased while suppressing damage to the wafer 200 by the raw material gas. Furthermore, the second or fourth film deposition process can be performed while the metal-containing substance Y has already been formed on the wafer 200, thus suppressing damage to the wafer 200. In addition, the metal-containing substance Y formed on the second surface 400 is easily removed in the second or fourth film deposition process, thus improving selectivity. Therefore, according to this modified example, both selectivity and film deposition rate can be improved while suppressing damage to the wafer 200.

[0140] For example, it can also be set that b < a. Specifically, it can also be such that the ratio R (corresponding to an example of b%) of the flow rate of the first gas supplied to the wafer 200 during the period Tc' of the second film forming process with respect to the total of the flow rates of the first gas and the second gas is less than the ratio R (corresponding to an example of a%) during the period Tc' of the first film forming process. In addition, it can also be such that the exposure amount of the first gas to the wafer 200 in step S31 of the second film forming process is less than the exposure amount of the first gas to the wafer 200 in step S21 of the first film forming process. In addition, it can also be such that the exposure amount of the second gas to the wafer 200 in step S31 of the second film forming process is more than the exposure amount of the second gas to the wafer 200 in step S21 of the first film forming process. For example, by performing the second film forming process in such a manner as to satisfy at least one of the above, it is possible to perform the second film forming process under conditions where it is less likely to form the metal-containing substance Y on the wafer 200 compared to the first film forming process, that is, under conditions where the metal-containing substance Y on the wafer is easily removed.

[0141] More specifically, it can also be such that the supply time of the second gas in the second film forming process is longer than the supply time of the first gas in the first film forming process. In addition, it can also be such that the supply flow rate of the second gas in the second film forming process is more than the supply flow rate of the first gas in the first film forming process. In addition, it can also be such that the flow rate of the inert gas supplied simultaneously with the second gas in the second film forming process is smaller than the flow rate of the inert gas supplied simultaneously with the first gas in the first film forming process. For example, by satisfying at least one of the above, in the second film forming process, it is possible to make the exposure amount of the first gas to the wafer 200 in step S31 less than the exposure amount of the first gas to the wafer 200 in step S21 of the first film forming process, or, in the second film forming process, it is possible to make the exposure amount of the second gas to the wafer 200 in step S31 more than the exposure amount of the second gas to the wafer 200 in step S21 of the first film forming process.

[0142] It should be noted that in the above-described manner and modification examples 1 to 3, the case where the supply of the raw material gas and the supply of the reaction gas are alternately and non-simultaneously performed in the film forming process has been described. The present invention is not limited to the above manner, and the supply of the raw material gas (that is, the supply of the first gas and the second gas) and the supply of the reaction gas can be at least partially simultaneous. In this case, at least a part of the same effects as those of the above manner can also be obtained.

[0143] In addition, in the above-described manner and modification examples 1 to 3, the case where the first gas and the second gas are supplied from the same nozzle 249a has been described. The present invention is not limited to the above manner, and the first gas and the second gas can also be supplied from different nozzles. In this case, at least a part of the same effects as those of the above manner can also be obtained.

[0144] Furthermore, in the above-described methods and variations 1 to 3, examples of forming films using a batch-type substrate processing apparatus that processes multiple substrates at a time were described. The present invention is not limited to the methods described above. For example, it can also be appropriately applied when forming films using a single-sheet substrate processing apparatus that processes one or more substrates at a time. Additionally, in the above-described methods, examples of forming films using a substrate processing apparatus with a hot-wall type processing furnace were described. The present invention is not limited to the methods described above, and it can also be appropriately applied when forming films using a substrate processing apparatus with a cold-wall type processing furnace.

[0145] When using these substrate processing apparatuses, each processing step and processing condition can be performed in the same manner and in the same way as described above and in the modified examples, and the same effect as described above and in the modified examples can be obtained.

[0146] The methods and variations 1 to 3 described above can be used in appropriate combinations. The processing steps and conditions can be set to be the same as those in the methods and variations described above.

[0147] The foregoing has specifically described the methods and variations of the present invention. However, the methods and variations of the present invention are not limited to the methods and variations described above, and various modifications can be made without departing from its spirit.

Claims

1. A substrate processing method comprising a film forming step of performing (a) and (b) below, and preferentially forming a film containing a metal element on a first surface compared to a second surface, (a): A process of performing (a1) supplying a first gas containing the metal element to the substrate and (a2) supplying a second gas containing the metal element to the substrate, thereby forming a metal-containing material containing the metal element on at least a portion of the substrate, wherein, The substrate is a substrate having a first surface as a first material and a second surface as a second material different from the first material; (b): The process of supplying reactive gases to the substrate. Wherein, (a) includes the period Tc during which (a1) and (a2) are performed at least partially simultaneously. The first gas etches the metal-containing material at a first rate. The second gas etches the metal-containing material at a second rate that is higher than the first rate.

2. The substrate processing method according to claim 1, wherein, (a2) ends after (a1).

3. The substrate processing method according to claim 1 or 2, wherein, (a2) begins after (a1).

4. The substrate processing method according to claim 1 or 2, wherein, Start (a2) before starting (a1).

5. The substrate processing method according to any one of claims 1 to 4, comprising: The first film-forming step of the aforementioned film-forming process; and After the first film-forming process, a second film-forming process is performed on the substrate under conditions that make it easier to remove the metal-containing substance compared to the first film-forming process.

6. The substrate processing method according to claim 5, wherein, In the second film-forming process, the ratio R of the flow rate of the first gas during the period Tc relative to the total flow rate of the first gas supplied to the substrate and the flow rate of the second gas is less than the ratio R in the first film-forming process.

7. The substrate processing method according to claim 5, wherein, The exposure amount of the first gas to the substrate in the second film-forming process (a1) is less than the exposure amount of the first gas to the substrate in the first film-forming process (a1).

8. The substrate processing method according to claim 5, wherein, The exposure of the second gas to the substrate in the second film-forming process (a2) is greater than the exposure of the second gas to the substrate in the first film-forming process (a2).

9. The substrate processing method according to any one of claims 1 to 8, comprising: Perform (a1) and (b), or do not perform (a2) the third film-forming process; and After the third film-forming process, the fourth film-forming process is performed.

10. The substrate processing method according to any one of claims 1 to 9, wherein, The metal element is a transition metal.

11. The substrate processing method according to any one of claims 1 to 10, wherein, The first gas and the second gas are gases containing halogen elements.

12. The substrate processing method according to any one of claims 1 to 11, wherein, The first gas is a gas composed of the metal element, the halogen element, and oxygen.

13. The substrate processing method according to any one of claims 1 to 12, wherein, The second gas is a gas containing the metal element and the halogen element but without oxygen.

14. The substrate processing method according to any one of claims 1 to 13, wherein, The film-forming process is carried out at a temperature above 200°C and below 650°C.

15. The substrate processing method according to any one of claims 1 to 14, wherein, A recess is formed on the surface of the substrate, the recess having a first surface at the bottom and a second surface on the sidewall. In the film-forming process, a film is embedded in the recess as the film formation.

16. A method for manufacturing a semiconductor device, comprising a film-forming step of performing (a) and (b) the following, preferentially forming a film containing a metal element on a first surface compared to a second surface, (a): A process of performing (a1) supplying a first gas containing the metal element to the substrate and (a2) supplying a second gas containing the metal element to the substrate, thereby forming a metal-containing material containing the metal element on at least a portion of the substrate, wherein, The substrate is a substrate having a first surface as a first material and a second surface as a second material different from the first material; (b): The process of supplying reactive gases to the substrate. Wherein, (a) includes the period Tc during which (a1) and (a2) are performed at least partially simultaneously. The first gas etches the metal-containing material at a first rate. The second gas etches the metal-containing material at a second rate that is higher than the first rate.

17. A substrate processing apparatus, comprising: A gas supply system that supplies a first gas containing a metallic element, a second gas containing the metallic element, and a reactant gas; and The control unit is configured to control the gas supply system to perform a process including (a) and (b) described below, and a film-forming process that preferentially forms a film containing the metal element on the first surface compared to the second surface. (a): Performing (a1) a process of supplying the first gas to the substrate and (a2) a process of supplying the second gas to the substrate, wherein a metal-containing substance comprising the metal element is formed on at least a portion of the substrate, wherein, The substrate is a substrate having a first surface as a first material and a second surface as a second material different from the first material; (b) Processing of supplying the reactant gas to the substrate. (a) includes the period Tc during which (a1) and (a2) are at least partially performed simultaneously. The gas supply system supplies a gas for etching the metal-containing material at a first rate as the first gas, and supplies a gas for etching the metal-containing material at a second rate higher than the first rate as the second gas.

18. A process article wherein a substrate processing apparatus is subjected to steps performed by a computer, the steps including a film-forming step of performing (a) and (b) below, and preferentially forming a film containing a metal element on a first surface compared to a second surface. (a): The steps of (a1) supplying a first gas containing the metal element to the substrate and (a2) supplying a second gas containing the metal element to the substrate are performed, thereby forming a metal-containing material containing the metal element on at least a portion of the substrate, wherein... The substrate is a substrate having a first surface as a first material and a second surface as a second material different from the first material; (b): The step of supplying reactive gas to the substrate. Wherein, (a) includes the period Tc during which (a1) and (a2) are performed at least partially simultaneously. The first gas etches the metal-containing material at a first rate. The second gas etches the metal-containing material at a second rate that is higher than the first rate.

Images