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

Abstract

To provide a technique capable of forming a film on a surface of a substrate preferentially to the other surface.SOLUTION: A first cycle in which (a1) a step of supplying first gas containing a first element to a substrate having a first surface and a second surface which are severally constituted of different substances, and forming a substance X containing the first element at at least a part of the substrate, and (a2) a step of supplying first reaction gas which reacts with the substance X to the substrate are performed non-simultaneously a first number of times; a film containing the first element is formed on at least a part of the substrate; incubation time of the first gas on the second surface is made longer than incubation time on the first surface; and at least a part of the substance X formed on the substrate is removed in (a1).SELECTED DRAWING: Figure 3

Description

[Technical field]

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

[0002] 2. Description of the Related Art As one step in the manufacturing process of a semiconductor device or a substrate processing process, a film may be formed preferentially on one surface of a substrate over other surfaces (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2018 / 179354 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides techniques that allow for preferential formation of films on certain surfaces of a substrate over other surfaces. [Means for solving the problem]

[0005] According to one aspect of the present disclosure, (a1) supplying a first gas containing a first element to a substrate having a first surface and a second surface each made of a different material, to form a material X containing the first element on at least a portion of the substrate; (a2) supplying a first reaction gas to the substrate, the first reaction gas reacting with the substance X; a first number of times to form a film containing the first element on at least a portion of the substrate; an incubation time of the first gas on the second surface is longer than an incubation time of the first gas on the first surface; In (a1), at least a portion of the substance X formed on the substrate is removed. Technology is provided. Effect of the Invention

[0006] The present disclosure allows for preferential formation of films on certain surfaces of a substrate over other surfaces. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic vertical cross-sectional view of a vertical processing furnace of a substrate processing apparatus according to one embodiment of the present disclosure. [Diagram 2] FIG. 2 is a schematic configuration diagram of a controller of a substrate processing apparatus according to one embodiment of the present disclosure, and is a block diagram showing a control system of the controller. [Diagram 3] FIG. 3 is a diagram illustrating a substrate processing process according to one embodiment of the present disclosure. [Figure 4] Fig. 4(A) is a diagram showing a state when a first gas is supplied to a substrate having a first surface and a second surface. Fig. 4(B) is a diagram showing a state in which a substance containing a first element is formed on the first surface and the second surface. Fig. 4(C) is a diagram showing a state in which the first gas removes the substance containing the first element formed on the substrate when the first gas is supplied to the substrate of Fig. 4(B). Fig. 4(D) is a diagram showing a state on the substrate after at least a part of the substance containing the first element has been removed. [Diagram 5] FIG. 5 is an image diagram for explaining a film formed on a substrate by a substrate processing step according to one embodiment of the present disclosure. [Figure 6] FIG. 6 is a diagram showing a substrate processing process according to the second embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, one embodiment of the present disclosure will be described mainly with reference to Figures 1 to 5. Note that all of the drawings used in the following description are schematic, and the dimensional relationships of the elements, the ratios of the elements, etc. shown in the drawings do not necessarily match the actual ones. Furthermore, the dimensional relationships of the elements, the ratios of the elements, etc. between multiple drawings do not necessarily match.

[0009] (1) Configuration of the substrate processing device 1, the process furnace 202 has a heater 207 as a heating system (temperature adjustment unit). The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas by heat.

[0010] 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 in a cylindrical shape with a closed upper end and an open lower end. A manifold 209 that supports the reaction tube 203 is disposed below the reaction tube 203. An O-ring 220a is provided as a sealing member between the manifold 209 and the reaction tube 203. The reaction tube 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 capable of accommodating one or more wafers 200 as substrates is formed inside the processing vessel.

[0011] Nozzles 249a and 249b are provided in the processing chamber 201 so as to penetrate a sidewall of the manifold 209. Gas supply pipes (pipes) 232a and 232b are connected to the nozzles 249a and 249b, respectively.

[0012] Gas supply pipes 232a and 232b are provided with mass flow controllers (MFCs) 241a and 241b, which are flow rate controllers (flow rate control parts), and valves 243a and 243b, which are on-off valves, in order from the upstream side. Gas supply pipes 232c and 232d, which supply inert gas, are connected to the gas supply pipes 232a and 232b downstream of the valves 243a and 243b. Gas supply pipes 232c and 232d are provided with MFCs 241c and 241d and valves 243c and 243d, respectively, in order from the upstream side.

[0013] The nozzles 249a and 249b are provided in a circular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, along the inner wall of the reaction tube 203 from the lower part to the upper part, so as to rise upward in the loading direction of the wafers 200. Gas supply holes 250a and 250b for supplying gas are provided on the side of the nozzles 249a and 249b, respectively. The gas supply holes 250a and 250b are each opened to face the center of the reaction tube 203, so that gas can be supplied toward the wafers 200. A plurality of gas supply holes 250a and 250b are provided from the lower part to the upper part of the reaction tube 203.

[0014] A first gas containing a first element is supplied from the gas supply pipe 232a into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.

[0015] A first reactive gas that reacts with a substance containing a first element is supplied from the gas supply pipe 232b into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.

[0016] An inert gas is supplied from the gas supply pipes 232c and 232d into the processing chamber 201 via the MFCs 241c and 241d, the valves 243c and 243d, the gas supply pipes 232a and 232b, and the nozzles 249a and 249b.

[0017] A first gas supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. A first reactive gas supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. The first gas supply system and the first reactive gas supply system may be collectively referred to as a gas supply system. An inert gas supply system is mainly composed of the gas supply pipes 232c and 232d, the MFCs 241c and 241d, and the valves 243c and 243d. The inert gas supply system may be included in the gas supply system.

[0018] Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which the valves 243a-243d, MFCs 241a-241d, etc. are integrated. The integrated supply system 248 is connected to the gas supply pipes 232a-232d, respectively, and configured such that the supply operation of various gases into the gas supply pipes 232a-232d, i.e., the opening and closing operation of the valves 243a-243d and the flow rate adjustment operation by the MFCs 241a-241d, etc., are controlled by a controller 121, which will be described later.

[0019] The reaction tube 203 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201. A vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit). The APC valve 244 is configured to be able to perform evacuation and stop evacuation in the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is in operation, and further, to adjust the pressure in the processing chamber 201 by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is in operation. An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

[0020] Below the manifold 209, a seal cap 219 is provided as a furnace port cover body capable of airtightly closing the lower end opening of the manifold 209. An O-ring 220b is provided on the upper surface of the seal cap 219 as a seal member that abuts against the lower end of the manifold 209. Below the seal cap 219, a rotation mechanism 267 is provided for rotating the boat 217 described below. A rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217 through the seal cap 219. The boat elevator 115 is configured to be able to load and unload the boat 217 into and out of the processing chamber 201 by raising and lowering the seal cap 219. The boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers the boat 217, i.e., the wafers 200, into and out of the processing chamber 201.

[0021] The boat 217 as a substrate support is configured to support multiple wafers, for example 25 to 200 wafers 200, in a horizontal position and aligned vertically with their centers aligned, i.e., arranged at intervals. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages. In this specification, a numerical range such as "25 to 200 sheets" means that the lower limit and the upper limit are included in the range. Therefore, for example, "25 to 200 sheets" means "25 sheets or more and 200 sheets or less". The same applies to other numerical ranges.

[0022] A temperature sensor 263 serving as a temperature detector is installed inside the reaction tube 203. By adjusting the power supply to the heater 207 based on temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 can have a 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.

[0023] As shown in FIG. 2, the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122 configured as, for example, a touch panel is connected to the controller 121. The substrate processing apparatus may be configured to include one control unit or multiple control units. That is, the control for performing the processing sequence described later may be performed using one control unit or multiple control units. The multiple control units may be configured as a control system connected to each other by a wired or wireless communication network, and the control for performing the processing sequence described later may be performed by the entire control system. When the term "control unit" is used in this specification, it may include one control unit, multiple control units, or a control system configured by multiple control units.

[0024] The storage device 121c is composed of, for example, a flash memory, a HDD (Hard Disk Drive), etc. A control program for controlling the operation of the substrate processing apparatus 100, a process recipe in which procedures and conditions of the substrate processing described later are described, etc. are readably stored in the storage device 121c. The process recipe is a combination of procedures in the substrate processing described later that are executed by the controller 121 to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are collectively referred to simply as a program. In addition, the process recipe is also simply referred to as a recipe. In this specification, when the word program is used, it may include only a recipe, only a control program, or both. The RAM 121b is configured as a memory area (work area) in which the programs, data, etc. read by the CPU 121a are temporarily stored.

[0025] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241d, the valves 243a to 243d, the pressure sensor 245, the APC valve 244, the vacuum pump 246, the heater 207, the temperature sensor 263, the rotation mechanism 267, the boat elevator 115, and the like.

[0026] The CPU 121a is configured to read and execute a control program from the storage device 121c, and also to read a recipe from the storage device 121c in response to an input of an operation command from the input / output device 122, etc. The CPU 121a is configured to control the flow rate adjustment operation of various gases by the MFCs 241a to 241d, the opening and closing operations of the valves 243a to 243d, the opening and closing operation of the APC valve 244 and the pressure adjustment operation by the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, etc., in accordance with the contents of the read recipe.

[0027] The controller 121 can be configured by installing the above-mentioned program stored in an external storage device (for example, a magnetic disk such as a hard disk, an optical disk such as a CD, a magneto-optical disk such as an MO, or a semiconductor memory such as a USB memory) 123 into a computer. The storage device 121c and the external storage device 123 are configured as computer-readable recording media on which the program is recorded. Hereinafter, these are collectively referred to simply as recording media. When the term recording media is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both of them. The program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0028] (2) Substrate processing An example of a processing sequence for forming a predetermined film on a first surface 300 of a wafer 200 having a first surface 300 and a second surface 400 each made of different materials, as one step of substrate processing in a manufacturing process of a semiconductor device, using the above-mentioned substrate processing apparatus 100 will be described with reference to Figures 3 to 5. In the following description, the operation of each part constituting the substrate processing apparatus 100 is controlled by a controller 121.

[0029] The first surface 300 and the second surface 400 have different materials exposed. Specifically, the first surface 300 is a so-called conductive film, which is a film made of a conductive material and has high electrical conductivity. The first surface 300 is, for example, a molybdenum (Mo) film, a titanium nitride (TiN) film, or the like. The second surface 400 is a film made of a non-conductive material and has lower electrical conductivity than the first surface. The second surface 400 is, for example, an oxide film such as a silicon oxide (SiO) film, or a semiconductor film. In this embodiment, a film 500 made of a conductive material is selectively formed on the first surface 300 of the wafer 200 having the first surface 300 and the second surface 400.

[0030] The term "wafer" used in this specification may mean the wafer itself or a laminate of the wafer and a predetermined layer or film formed on its surface. The term "surface of a wafer" used in this specification may mean the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. When described in this specification, "forming a predetermined layer on a wafer" may mean forming a predetermined layer directly on the surface of the wafer itself or forming a predetermined layer on a layer or the like formed on the wafer. When used in this specification, the term "substrate" is synonymous with the term "wafer".

[0031] (Wafer loading) 1, when a plurality of wafers 200 are loaded into the boat 217 (wafer charge), the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115, carried into the processing chamber 201 (boat load), and accommodated in the processing vessel. In this state, the seal cap 219 closes the lower end opening of the manifold 209 via the O-ring 220b.

[0032] (Pressure and temperature regulation) The inside of the processing chamber 201, i.e., the space in which the wafer 200 exists, is evacuated by the vacuum pump 246 so as to reach a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled (pressure adjustment) based on the measured pressure information. The vacuum pump 246 is kept in a constantly operating state at least until the processing of the wafer 200 is completed. Also, the inside of the processing chamber 201 is heated by the heater 207 so as to reach a desired temperature. At this time, the amount of electricity supplied to the heater 207 is feedback-controlled (temperature adjustment) based on temperature information detected by the temperature sensor 263 so as to achieve a desired temperature distribution inside the processing chamber 201. The heating inside the processing chamber 201 by the heater 207 is continued at least until the processing of the wafer 200 is completed.

[0033] (First gas supply, step S11) First, a first gas containing a first element is supplied to the wafer 200 in the processing chamber 201. Specifically, the valve 243a is opened to allow the first gas to flow into the gas supply pipe 232a. The flow rate of the first gas is adjusted by the MFC 241a, and the first gas is supplied into the processing chamber 201 through the nozzle 249a and exhausted from the exhaust pipe 231. At the same time, the valve 243c is opened to allow an inert gas to flow into the gas supply pipe 232c. The flow rate of the inert gas is adjusted by the MFC 241c, and the inert gas is supplied into the processing chamber 201 together with the first gas and exhausted from the exhaust pipe 231. In addition, in order to prevent the first gas from entering the nozzle 249b, the valve 243d is opened to allow the inert gas to flow into the gas supply pipe 232d. The inert gas is supplied into the processing chamber 201 through the gas supply pipe 232d and the nozzle 249b and exhausted from the exhaust pipe 231. At this time, the main gas flowing inside the processing chamber 201 is a first gas containing a first element.

[0034] The processing conditions in step S11 are as follows: Temperature of wafer 200: 300 to 700°C First gas supply time: 1 to 60 seconds Partial pressure of first gas: 10~10000Pa Examples are given below.

[0035] By supplying the first gas, a substance X containing a first element is formed on at least a part of the wafer 200. Here, the substance X is at least one of the following: a molecule of the first gas chemically or physically adsorbed on the surface of the wafer 200 and / or a part of the molecular structure of the first gas, which contains the first element, a compound containing the first element chemically bonded with other elements, or a reduced simple substance of the first element. Specifically, when a metal-containing gas is used as the first gas, the substance X is at least one of the following: a molecule of the metal-containing gas and / or a part of the molecular structure of the metal-containing gas, which contains a metal element, a compound containing a metal element chemically bonded with other elements, or a reduced simple substance of the metal element. More specifically, for example, the substance X is a molecule of a Mo-containing gas, a part of the molecular structure of a Mo-containing gas, Mo, etc.

[0036] 4(A) to 4(D) are conceptual diagrams for explaining the state on the wafer 200 in this step.

[0037] In this embodiment, the incubation time of the first gas on the second surface 400 is set longer than the incubation time of the first gas on the first surface 300. Therefore, the amount of substance X containing the first element formed on the first surface 300 is greater than the amount of substance X containing the first element formed on the second surface 400. Here, the incubation time refers to the time required from the start of the supply of gas to a surface until gas molecules start to adsorb or a film starts to form on the surface.

[0038] That is, it takes a longer time for molecules of the first gas to start being adsorbed on the second surface 400 than on the first surface 300. For this reason, even if the first gas is supplied onto the wafer 200 having the first surface 300 and the second surface 400 as shown in Fig. 4(A), substance X is less likely to be formed on the second surface 400 than on the first surface 300.

[0039] However, for example, even if the supply time of the first gas in this step is set to a time equal to or shorter than the incubation time of the first gas on the second surface 400, as shown in Fig. 4(B), a substance X containing the first element may be formed on a part of the second surface 400, causing a selectivity breakdown. Then, with each processing cycle, the substance X containing the first element may grow larger around the selectivity breakdown, and the substance X may be formed on the second surface 400 as well.

[0040] Here, the first gas has a property of removing the substance X. As a result, in this step, the substance X containing the first element formed on the wafer 200 as shown in Figures 4(C) and 4(D) is removed at the same time as the substance X containing the first element is formed.

[0041] In this embodiment, the amount of substance X formed per unit time on the first surface 300 is set to exceed the amount of substance X removed per unit time. Furthermore, the amount of substance X formed per unit time on the second surface 400 is set to be less than the amount of substance X removed per unit time. This makes it possible in this step to make substance X more likely to form on the first surface 300 and less likely to form on the second surface 400, as shown in Fig. 4(D).

[0042] As described above, in this step, due to the difference in incubation time of the first gas between the first surface 300 and the second surface 400, and the removal of the substance X containing the first element, the substance X containing the first element is formed preferentially on the first surface 300 rather than on the second surface 400.

[0043] Alternatively, the first gas may have the effect of forming a substance X containing the first element on the first surface 300 while etching the substance X. In other words, in the technology disclosed herein, the first gas may form the substance X on the first surface 300 while etching the substance X on the second surface 400. This makes it possible to selectively form the substance X containing the first element on the first surface 300 even if the selective breaks are not removed by an additional process such as a process of etching the substance X.

[0044] This step may be performed under conditions where a substance X containing the first element can be formed on at least a portion of the second surface 400. This makes it easier for selective breaks to form on the second surface 400, but it is possible to increase the amount of the substance X containing the first element formed on the first surface 300 per unit time. Even in such a case, the selective breaks on the second surface 400 are removed by removing the substance X containing the first element in this step. Therefore, by performing this step under conditions where a substance X containing the first element can be formed on at least a portion of the second surface 400, it is possible to increase the amount of the substance X formed on the first surface 300 per unit time and obtain good selectivity.

[0045] According to verification by the present inventors, it has been confirmed that in this step, the substance X containing the first element formed on the second surface 400 is removed preferentially over the second surface 400 (i.e., the non-conductive substance). In other words, the etching rate of the non-conductive substance by the first gas is lower than the etching rate of the conductive substance. This makes it possible to remove the selective breakage of the substance X on the second surface 400 without damaging the non-conductive substance that constitutes the second surface 400.

[0046] As the first gas, a gas containing a metal element as the first element and a halogen element can be used.

[0047] As the metal element, for example, a metal element of the 4th to 6th periods and of the 3rd to 14th groups can be used. Preferably, a transition metal element of the 3rd to 12th groups can be used as the metal element. In this case, the effect of this embodiment can be more effectively obtained. More preferably, a transition metal element of the 5th period can be used as the metal element. In this case, the effect of this embodiment can be more effectively obtained. As the transition metal element of the 5th period, for example, Mo can be used. In this case, the effect of this embodiment can be particularly easily obtained.

[0048] Examples of halogen elements that can be used include chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. One or more of these can be used as the halogen element.

[0049] Specifically, the first gas may be, for example, a gas containing Mo and Cl. In this case, the effect of this embodiment is particularly easily obtained. As the gas containing Mo and Cl, for example, a gas containing any one of molybdenum dichloride (MoO2Cl2) gas, molybdenum oxide tetrachloride (MoOCl4) gas, molybdenum pentachloride (MoCl5) gas, molybdenum tetrachloride (MoCl4) gas, etc., or a gas containing one or more of these may be used.

[0050] Furthermore, when a gas containing Cl and a fifth period transition metal element having an electron orbit similar to that of Mo is used as the first gas, it becomes easier to obtain the same effect as when a gas containing Mo and Cl is used. As the fifth period transition metal element, for example, yttrium (Y), zirconium (Zr), niobium (Nb), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), etc. can be used.

[0051] As the inert gas, for example, in addition to nitrogen (N2) gas, rare gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas, etc., can be used. One or more of these can be used as the inert gas.

[0052] (Purge, step S12) After a substance X containing a first element is formed on at least a portion of the wafer 200, the valves 243a and 243b are closed, and the valves 243c and 243d are opened to supply an inert gas as a purge gas into the gas supply pipes 232a and 232b via the gas supply pipes 232c and 232d. At the same time, the APC valve 244 of the exhaust pipe 231 is kept open, and the processing chamber 201 is evacuated to a vacuum by the vacuum pump 246, and the processing chamber 201 is purged.

[0053] (First reactive gas supply, step S13) Next, a first reactive gas is supplied to the wafer 200 in the processing chamber 201. Specifically, the valve 243b is opened to allow the first reactive gas to flow into the gas supply pipe 232b. The flow rate of the first reactive gas is adjusted by the MFC 241b, and the first reactive gas is supplied into the processing chamber 201 through the nozzle 249b and exhausted from the exhaust pipe 231. At the same time, the valve 243d is opened to allow the inert gas to flow into the gas supply pipe 232d. The flow rate of the inert gas is adjusted by the MFC 241d, and the first reactive gas is supplied into the processing chamber 201 together with the first reactive gas and exhausted from the exhaust pipe 231. In addition, in order to prevent the first reactive gas from entering the nozzle 249a, the valve 243c is opened to allow the inert gas to flow into the gas supply pipe 232c. The inert gas is supplied into the processing chamber 201 through the gas supply pipe 232c and the nozzle 249a and exhausted from the exhaust pipe 231. At this time, the main gas flowing into the processing chamber 201 is the first reaction gas.

[0054] The processing conditions in step S13 are as follows: Temperature of wafer 200: 300 to 700°C Supply time of first reaction gas: 0.01 to 600 seconds Partial pressure of first reactant gas: 4000~13000Pa Examples are given below.

[0055] The first reactive gas may be, for example, a gas that reacts with the substance X containing the first element and has a reducing effect against the first gas. The first reactive gas may be, for example, hydrogen (H2) gas, deuterium (D2) gas, borane (BH3) gas, diborane (B2H6) gas, carbon monoxide (CO) gas, ammonia (NH3) gas, monosilane (SiH4) gas, disilane (Si2H6) gas, trisilane (Si3H8) gas, monogermane (GeH4) gas, digermane (Ge2H6) gas, or the like.

[0056] As the first reactive gas, in addition to the reducing gas, for example, a gas containing a nitriding gas, a sulfiding gas, a selenide gas, a telluride gas, etc., which reacts with the substance X to form a conductive substance, can be used. For example, when the first reactive gas is any one of a nitriding gas, a sulfiding gas, a selenide gas, and a telluride gas, a nitride film, a sulfiding film, a selenide film, and a telluride film can be formed on the wafer.

[0057] As the nitriding gas, for example, one or more of hydrogen nitride gases such as NH3 gas, diazene (N2H2) gas, and hydrazine (N2H4) gas can be used. As the sulfurizing gas, for example, gases including sulfane (H2S), disulfane (H2S2), diammonium sulfide ((NH4)2S), dimethyl sulfide ((CH3)2S), etc. can be used. As the sulfurizing gas, for example, one or more of these can be used. As the selenizing gas, for example, gases including selenium (H2Se), diselane (H2Se2), dimethylselenium ((CH3)2Se), etc. can be used. As the selenizing gas, for example, one or more of these can be used. As the tellurizing gas, for example, gases including terane (H2Te), diterane (H2Te2), dimethylterene ((CH3)2Te), etc. can be used. As the tellurizing gas, for example, one or more of these can be used.

[0058] (Purge, step S14) After a layer containing a first element constituted by the substance X is formed on the wafer 200, an inert gas is supplied as a purge gas by a process procedure similar to that of step S12 described above, and the inside of the processing chamber 201 is evacuated to a vacuum by the vacuum pump 246 while the APC valve 244 of the exhaust pipe 231 is kept open, and the inside of the processing chamber 201 is purged.

[0059] (Performed a predetermined number of times, step S15) A first cycle in which the above-mentioned steps S11 to S14 are non-simultaneously performed is performed a first number of times (n, n is an integer of 1 or 2 or more). The first cycle is performed, for example, 1 to 200 times. As a result, as shown in FIG. 5, a film 500 containing a first element is formed on the first surface 300, which is at least a part of the wafer 200 and has a first surface 300 and a second surface 400.

[0060] The film 500 containing the first element is a film made of a conductive material. As a film made of a conductive material, for example, a metal-containing film containing a metal element is formed. As a metal-containing film, for example, a Mo-containing film is formed.

[0061] Here, when the first gas supply and the first reactive gas supply are performed simultaneously, a substance X containing a first element is formed on the wafer 200 by a reaction between the first gas and the first reactive gas in the gas phase. In this case, the gas is likely to be consumed by the reaction between the first gas and the first reactive gas at a portion of the wafer surface where the gas can easily reach, while the first gas and the first reactive gas are unlikely to be sufficiently supplied to a portion where the gas cannot easily reach. Therefore, a difference in thickness is likely to occur in the film formed on the wafer surface.

[0062] In this embodiment, the first gas and the first reactive gas are supplied asynchronously, so that a sufficient amount of the first gas reaches a portion that is difficult for the gas to reach, and then the reaction with the first reactive gas occurs, thereby improving the uniformity of the film thickness on the wafer surface.

[0063] When, for example, MoCl5 gas is used as the first gas and, for example, H2 gas is used as the first reactive gas, the MoCl5 gas and the H2 gas react with each other, whereby Cl in the MoCl5 gas is reduced by the H2 gas, and a molybdenum (Mo)-containing film, which is a metal-containing film, is formed as the substance X on the first surface 300 of the wafer 200. At this time, reaction by-products such as hydrogen chloride (HCl) and Cl2 are generated. By purging between the supply of the first gas and the supply of the first reactive gas, gases and reaction by-products remaining in the process chamber 201 are removed.

[0064] (After purging and atmospheric pressure recovery) An inert gas is supplied into the processing chamber 201 from each of the gas supply pipes 232c and 232d, and exhausted from the exhaust pipe 231. The inert gas acts as a purge gas. This purges the processing chamber 201, and gas and reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (after-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

[0065] (Wafer removal) The seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafers 200 supported by the boat 217 are unloaded from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). The processed wafers 200 are removed from the boat 217 (wafer discharging).

[0066] (3) Other aspects Next, other aspects of the substrate processing process and the substrate processing apparatus in the above-mentioned embodiment will be described in detail. In the following embodiments, only the points different from the above-mentioned embodiment will be described in detail.

[0067] (Second aspect) In this embodiment, for example, a second gas supply system and a second reactive gas supply system are added to the above-mentioned substrate processing apparatus 100. Specifically, for example, a second gas supply pipe 232e for supplying a second gas is connected to the downstream side of the valve 243a of the gas supply pipe 232a and the upstream side of a connection part with the gas supply pipe 232c. Also, a second reactive gas supply pipe 232f for supplying a second reactive gas is connected to the downstream side of the valve 243b of the gas supply pipe 232b and the upstream side of a connection part with the gas supply pipe 232d. The gas supply pipes 232e and 232f are respectively provided with MFCs 241e and 241f and valves 243e and 243f in this order from the upstream side. The gas supply pipe 232e, the MFC 241e, and the valve 243e constitute a second gas supply system. The gas supply pipe 232f, the MFC 241f, and the valve 243f constitute a second reactive gas supply system.

[0068] In this embodiment, as shown in Fig. 6, after performing the first cycle n times in which the above-mentioned steps S11 to S15 are performed non-simultaneously, the second cycle m times in which the steps S21 to S25 are performed non-simultaneously. That is, the second cycle with different conditions from the first cycle is further performed. In this manner, a film containing the first element is selectively formed on the first surface 300 of the wafer 200, thereby optimizing the selectivity and the film formation rate.

[0069] (Second gas supply, step S21) After performing the above-mentioned steps S11 to S15 to form a film containing the first element on at least a part of the wafer 200, a second gas containing the first element is supplied to the wafer 200 in the processing chamber 201. Specifically, the valve 243e is opened to allow the second gas to flow into the gas supply pipe 232e. The flow rate of the second gas is adjusted by the MFC 241e, and the second gas is supplied into the processing chamber 201 through the nozzle 249a and exhausted from the exhaust pipe 231. At the same time, the valve 243c is opened to allow the inert gas to flow into the gas supply pipe 232c. The flow rate of the inert gas is adjusted by the MFC 241c, and the inert gas is supplied into the processing chamber 201 together with the second gas and exhausted from the exhaust pipe 231. In addition, in order to prevent the second gas from entering the nozzle 249b, the valve 243d is opened to allow the inert gas to flow into the gas supply pipe 232d. The inert gas is supplied into the processing chamber 201 via the gas supply pipe 232 d and the nozzle 249 b , and is exhausted from the exhaust pipe 231 .

[0070] At this time, the main gas flowing in the processing chamber 201 is a second gas containing a first element. As the second gas, for example, a gas containing a metal element as the first element and a halogen element can be used. As the second gas, one or more of the gases exemplified as the first gas can be used.

[0071] Here, in this embodiment, the "substance X containing one element" used in the above embodiment further includes "at least one of the following among molecules of the second gas chemically or physically adsorbed on the surface of the wafer 200 and / or a part of the molecular structure of the second gas: one containing the first element, a compound containing the first element chemically bonded with another element, or a reduced simple substance of the first element." In step S21, the second gas is supplied to form the substance X containing the first element on at least a part of the wafer 200.

[0072] Here, the incubation time of the second gas on the first surface 300 may be different from the incubation time on the second surface 400. For example, the incubation time of the second gas on the second surface 400 may be longer than that on the first surface 300. This makes it possible to selectively form a film on the first surface 300 with respect to the second surface 400 even in the second cycle, thereby improving selectivity.

[0073] Also, in step S21, at least a part of the substance X formed on the wafer 200 may be removed. Also, the ease of removal of the substance X may be different between steps S11 and S21. Hereinafter, an example will be described in which step S21 is performed under conditions in which the substance X is more easily removed than step S11 (in other words, the second cycle is performed under conditions in which the substance X is more easily removed than the first cycle).

[0074] In step S21, an example of a condition for making the substance X formed on the wafer 200 easier to remove than in step S11 is to use, as the second gas, a gas that is more reactive with the substance X containing a first element formed on the wafer 200 than the first gas. That is, by using a gas different from the first gas as the second gas, it is possible to change the ease of removal of the substance X containing a first element in the first cycle using the first gas and the second cycle using the second gas.

[0075] As the second gas having a higher reactivity with the substance X containing the first element than the first gas, for example, a gas containing a larger number of halogen elements in one molecule than the above-mentioned first gas can be used. When MoO2Cl2 gas is used as the first gas, for example, MoCl5 gas can be used as the second gas.

[0076] In step S11, the process conditions when MoO2Cl2 gas is used as the first gas are as follows: Wafer 200 temperature: 300 to 700°C First gas supply time: 1 to 60 seconds Partial pressure of first gas: 10~10000Pa 1st number of times: 1 to 200 times Examples are given below.

[0077] In step S21, the process conditions when MoCl5 gas is used as the second gas are as follows: Temperature of wafer 200: 300 to 700°C Second gas supply time: 1 to 60 seconds Second gas partial pressure: 10~10000Pa Second number of times: 1 to 50 times Examples are given below.

[0078] An example of a condition for making the substance X formed on the wafer 200 easier to remove in step S21 than in step S11 is to make the partial pressure of the second gas in the processing chamber 201 (in the space in which the wafer 200 exists) in step S21 higher than the partial pressure of the first gas in the processing chamber 201 in step S11. In this way, by changing the partial pressures in steps S11 and S21, it is possible to change the ease with which the substance X containing the first element is removed in the first cycle and the second cycle. In this case, even if gases having the same molecular structure are used as the first gas and the second gas, it is possible to change the ease with which the substance X containing the first element is removed in the first cycle and the second cycle.

[0079] When the substance X containing the first element formed on the wafer 200 is removed, other conductive substances, for example, the conductive substance constituting the first surface 300, may also be removed. As in this embodiment, by performing the first cycle and the second cycle in which the ease of removal of the substance containing the first element differs, it is possible to suppress damage to the other conductive substances and optimize the selectivity and the film formation rate.

[0080] For example, the first cycle is performed first, and then the second cycle is performed. In this case, in the first cycle, since the substance X containing the first element is relatively difficult to remove, it is possible to form the substance X containing the first element on the first surface 300 while suppressing damage to the conductive substance constituting the first surface 300 (etching of the conductive substance). Then, in the second cycle, since the substance X containing the first element has already been formed on the first surface 300, it becomes difficult for the conductive substance constituting the first surface 300 to be removed. In other words, it is possible to suppress damage to conductive substances other than the substance X.

[0081] In addition, some gases having the first element may have a low vapor pressure, because the substance X containing the first element is easily removed and therefore a film may be easily formed with good selectivity. For example, MoCl5 gas is a gas that easily forms a film with good selectivity, but has a low vapor pressure, compared to MoO2Cl2 gas. When processing a wafer 200 having a large surface area using such a gas, it may be difficult to supply a sufficient amount of gas to process the entire surface of the wafer 200. In this embodiment, a gas that easily forms a film with good selectivity on the wafer 200 and has a low vapor pressure, and a gas that has a high vapor pressure and does not easily form a film with good selectivity are used. This allows a film containing the first element to be formed on the first surface 300 with good selectivity, even when the surface area of ​​the wafer 200 is large. It is preferable that the conditions of each step are set so that the consumption of the gas that easily forms a film with good selectivity on the wafer 200 and has a low vapor pressure is less than the consumption of the gas that has a high vapor pressure and does not easily form a film with good selectivity throughout the entire substrate processing.

[0082] (Purge, step S22) After the substance X containing the first element is formed on at least a portion of the wafer 200, an inert gas is supplied as a purge gas by a process procedure similar to that of step S12 described above, and the inside of the processing chamber 201 is evacuated to a vacuum by the vacuum pump 246 while the APC valve 244 of the exhaust pipe 231 is kept open, and the inside of the processing chamber 201 is purged.

[0083] (Second reactant gas supply, step S23) Next, a second reactive gas is supplied to the wafer 200 in the processing chamber 201. Specifically, the valve 243f is opened to allow the second reactive gas to flow into the gas supply pipe 232f. The flow rate of the second reactive gas is adjusted by the MFC 241f, and the second reactive gas is supplied into the processing chamber 201 through the nozzle 249b and exhausted from the exhaust pipe 231. At the same time, the valve 243d is opened to allow an inert gas to flow into the gas supply pipe 232d. The flow rate of the inert gas is adjusted by the MFC 241d, and the second reactive gas is supplied into the processing chamber 201 together with the second reactive gas and exhausted from the exhaust pipe 231. In addition, in order to prevent the second reactive gas from entering the nozzle 249a, the valve 243c is opened to allow the inert gas to flow into the gas supply pipe 232c. The inert gas is supplied into the processing chamber 201 through the gas supply pipe 232c and the nozzle 249a and exhausted from the exhaust pipe 231. At this time, the main gas flowing into the processing chamber 201 is the second reactive gas.

[0084] The second reactive gas may be, for example, a gas that reacts with the substance X containing the first element and has a reducing effect against the second gas. Also, the second reactive gas may be, for example, a gas that reacts with the substance X to form a conductive substance, among gases including a nitriding gas, a sulfide gas, a selenide gas, a telluride gas, etc. The second reactive gas may be one or more of the gases exemplified as the first reactive gas.

[0085] (Purge, step S24) After a layer containing the first element is formed on the wafer 200, an inert gas is supplied as a purge gas by a process procedure similar to that of step S12 described above, and the APC valve 244 of the exhaust pipe 231 is kept open, and the processing chamber 201 is evacuated to a vacuum by the vacuum pump 246, thereby purging the processing chamber 201.

[0086] (Performed a predetermined number of times, step S25) By performing the second cycle, in which the above-mentioned steps S21 to S24 are performed non-simultaneously, a second number of times (m, where m is an integer of 1 or 2 or more), a film containing a first element of a predetermined thickness is formed on at least a portion of the wafer 200, that is, on the first surface 300.

[0087] In this embodiment, the second gas may be the same as the first gas. In this modification, the same effect as the above embodiment can be obtained. In this modification, the second gas supply system does not need to be a gas supply system different from the first gas supply system, so the device configuration can be simplified.

[0088] The second embodiment has been described by taking as an example a case where the first cycle including steps S11 to S15 is performed n times, and then the second cycle including steps S21 to S25, in which the substance X is more easily removed than in the first cycle, is performed m times. However, this embodiment is not limited to this. For example, the second cycle including steps S21 to S25, in which the substance X is more easily removed than in the first cycle, may be performed m times, and then the first cycle including steps S11 to S15 may be performed n times.

[0089] In this case, in the first cycle, since the substance X is easily removed, the selectivity breakdown on the second surface 400 is easily removed. In the second cycle, since there is almost no selectivity breakdown on the second surface, selectivity breakdown is unlikely to occur even if a second gas with low etching properties is used. In contrast, the substance X is unlikely to be removed on the first surface. In other words, the selectivity and the film formation rate can be improved.

[0090] (Third aspect) In this embodiment, a processing cycle including a first cycle in which steps S11 to S15 in the second embodiment described above are performed a first number of times (n times, n is an integer of 1 or 2 or more) and a second cycle in which steps S21 to S25 are performed a second number of times (m times, m is an integer of 1 or 2 or more) is performed is performed a plurality of times. The processing cycles performed from the Nth time (N is an integer of 2 or more) onwards are performed under conditions that make it easier to remove the substance X containing the first element formed on the wafer 200, compared to the N-1th time.

[0091] In this manner, it is possible to combine the N-1th or earlier process cycles in which the ease of removal of the substance X containing the first element is different, with the Nth or later process cycles, thereby optimizing the selectivity and film formation rate while suppressing damage to other conductive substances.

[0092] For example, the Nth or later processing cycle may be different from the N-1th or earlier processing cycle in at least one of the first number of times and the second number of times. Also, for example, the Nth or later processing cycle may be different from the N-1th or earlier processing cycle in at least one of the supply time of the first gas in step S11 and the supply time of the second gas in step S21. Also, for example, the Nth or later processing cycle may be different from the N-1th or earlier processing cycle in at least one of the partial pressure of the first gas in the processing chamber 201 in step S11 and the partial pressure of the second gas in the processing chamber 201 in step S21. By performing at least one of these, the ease of removal of the substance X containing the first element can be changed between processing cycles.

[0093] For example, the substance X containing the first element is made easier to remove in the Nth and subsequent treatment cycles than in the N-1th and previous treatment cycles. In this case, since the substance X containing the first element is relatively difficult to remove in the N-1th and previous treatment cycles, the substance X containing the first element can be formed on the first surface 300 while suppressing damage to other conductive substances. Then, in the Nth and subsequent treatment cycles, the substance X containing the first element has already been formed on the first surface 300, so the conductive substance constituting the first surface 300 becomes difficult to remove. In other words, a film containing the first element can be formed with good selectivity while suppressing damage to conductive substances other than the substance X.

[0094] Specifically, for example, in order to make it easier to remove the substance X containing the first element in the Nth or later processing cycle than in the N-1th or earlier processing cycle, the supply time of the second gas in the Nth or later processing cycle is made longer than the supply time of the second gas in the N-1th or earlier processing cycle.

[0095] In order to make it easier to remove the substance X containing the first element in the Nth or later processing cycle than in the N-1th or earlier processing cycle, the first number of times in the Nth or later processing cycle may be made smaller than the first number of times in the N-1th or earlier processing cycle. Also, the second number of times in the Nth or later processing cycle may be made larger than the second number of times in the N-1th or earlier processing cycle. Also, the supply time of the first gas in the Nth or later processing cycle may be made shorter than the supply time of the first gas in the N-1th or earlier processing cycle. Also, the partial pressure of the first gas in the Nth or later processing cycle may be made smaller than the partial pressure of the first gas in the N-1th or earlier processing cycle. Also, the partial pressure of the second gas in the Nth or later processing cycle may be made larger than the partial pressure of the second gas in the N-1th or earlier processing cycle.

[0096] Also, the substance containing the first element may be removed more easily in the N-1th or earlier processing cycle than in the Nth or later processing cycle. That is, the substance X containing the first element may be removed less easily in the Nth or later processing cycle than in the N-1th or earlier processing cycle. In order to make the substance X containing the first element more difficult to remove in the Nth or later processing cycle than in the N-1th or earlier processing cycle, the first number of times in the Nth or later processing cycle may be made larger than the first number of times in the N-1th or earlier processing cycle. Also, the second number of times in the Nth or later processing cycle may be made smaller than the second number of times in the N-1th or earlier processing cycle. Also, the supply time of the first gas in the Nth or later processing cycle may be made longer than the supply time of the first gas in the N-1th or earlier processing cycle. Also, the supply time of the second gas in the Nth or later processing cycle may be made shorter than the supply time of the second gas in the N-1th or earlier processing cycle. Also, the partial pressure of the first gas in the Nth or later processing cycle may be made larger than the partial pressure of the first gas in the N-1th or earlier processing cycle. Furthermore, the partial pressure of the second gas after the Nth time may be set to be lower than the partial pressure of the second gas before the (N-1)th time.

[0097] In this case, in the N-1th or earlier processing cycle, the substance X is easily removed, and therefore the selectivity breakdown on the second surface 400 is easily removed. In the Nth and subsequent processing cycles, the selectivity breakdown is hardly present on the second surface 400, and therefore the selectivity breakdown is unlikely to occur even when a second gas with low etching properties is used. In contrast, the substance X is unlikely to be removed on the first surface 300. In other words, the selectivity and the film formation rate can be improved.

[0098] In the above-mentioned embodiment, an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at a time has been described. The present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a single-wafer type substrate processing apparatus that processes one or several substrates at a time. In addition, in the above-mentioned embodiment, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a substrate processing apparatus having a cold-wall type processing furnace.

[0099] The above-mentioned processing sequences may be performed consecutively (in-situ) in the same processing chamber (processing vessel). At least one of the above-mentioned processing sequences and another processing may be performed in different processing chambers (processing vessels) (ex-situ). In either case, the same effects as those of the above-mentioned embodiment can be obtained. When these processings are performed in-situ, contamination of the substrate and changes in the surface state of the substrate that may occur due to the substrate being carried out of the processing chamber between processings or carried in from outside the processing chamber can be suppressed. When these processings are performed in-situ, the transition time between processings can be shortened. On the other hand, when these processings are performed ex-situ, the processings can be performed in parallel in different processing chambers, thereby increasing productivity.

[0100] When using these substrate processing apparatuses, each process can be performed according to the same process procedures and under the same process conditions as in the above-described aspects and modifications, and the same effects as in the above-described aspects and modifications can be obtained.

[0101] The above-mentioned aspects and modifications may be used in appropriate combination. The processing procedures and processing conditions in such a case may be the same as those of the above-mentioned aspects and modifications.

[0102] The above describes the aspects and modifications of the present disclosure in detail. However, the aspects and modifications of the present disclosure are not limited to the above aspects and modifications, and various changes can be made without departing from the spirit of the present disclosure. [Explanation of symbols]

[0103] 200 wafers (substrates)

Claims

1. (a1) supplying a first gas containing a first element to a substrate having a first surface and a second surface each made of a different material, and forming a material X containing the first element on at least a portion of the substrate; (a2) supplying a first reaction gas to the substrate, the first reaction gas reacting with the substance X; a first number of times to form a film containing the first element on at least a portion of the substrate; an incubation time of the first gas on the second surface is longer than an incubation time of the first gas on the first surface; In (a1), at least a portion of the substance X formed on the substrate is removed; A method for processing a substrate.

2. The substrate processing method according to claim 1 , wherein (a1) is performed under conditions that allow the substance X to be formed on at least a portion of the second surface.

3. the first surface is made of a conductive material; the second surface is made of a non-conductive material; The film is made of a conductive material. The method for processing a substrate according to claim 1 .

4. 4. The substrate processing method according to claim 3, wherein in (a1), the material X formed on the second surface is removed preferentially with respect to the non-conductive material.

5. (b1) supplying a second gas containing the first element to the substrate to form the substance X on at least a portion of the substrate; (b2) supplying to the substrate a second reaction gas that reacts with the substance X; a second number of times, The method for processing a substrate according to claim 1 .

6. The substrate processing method of claim 5 , wherein an incubation time of the second gas on the second surface is longer than an incubation time of the second gas on the first surface.

7. In (b1), at least a portion of the substance X formed on the substrate is removed; (b1) is performed under conditions that make it easier to remove the substance X formed on the substrate than (a1); The substrate processing method according to claim 5 .

8. 8. The substrate processing method according to claim 7, wherein a partial pressure of the second gas in a space in which the substrate is present in (b1) is greater than a partial pressure of the first gas in a space in which the substrate is present in (a1).

9. The substrate processing method according to claim 7 , wherein the second gas has a higher reactivity with the substance X formed on the substrate than the first gas.

10. performing a processing cycle including the first cycle performed a first number of times and the second cycle performed a second number of times a plurality of times; 8. The substrate processing method according to claim 7, wherein the processing cycles performed after an Nth time (N is an integer of 2 or more) are performed under conditions that make it easier for the substance X formed on the substrate to be removed, compared with the processing cycles up to (N-1) times.

11. 11. The substrate processing method according to claim 10, wherein at least one of the first number of times and the second number of times is different in the processing cycles performed after the Nth time compared to the N-1th time and before.

12. 11. The substrate processing method according to claim 10, wherein at least one of a supply time of the first gas in (a1) and a supply time of the second gas in (b1) is different in the processing cycles performed after the Nth time compared to the N-1th time and before.

13. 11. The substrate processing method of claim 10, wherein at least one of the partial pressure of the first gas in the space in which the substrate is present at (a1) and the partial pressure of the second gas in the space in which the substrate is present at (b1) is different in the processing cycles performed after the Nth processing cycle, compared to the N-1th processing cycles and before.

14. 14. The substrate processing method according to claim 1, wherein the first gas contains a metal element as the first element and a halogen element.

15. The substrate processing method according to claim 14 , wherein the metal element is a fifth period transition metal element.

16. The substrate processing method according to claim 14 , wherein the halogen element is chlorine.

17. The first gas is MoO ２ C ２ Gas, MoOCl ４ Gas, MoCl ５ Gas, MoCl ４ 15. The method of claim 14, wherein the gas is any one of:

18. (a1) supplying a first gas containing a first element to a substrate having a first surface and a second surface each made of a different material, and forming a material X containing the first element on at least a portion of the substrate; (a2) supplying a first reaction gas to the substrate, the first reaction gas reacting with the substance X; a first number of times to form a film containing the first element on at least a portion of the substrate; an incubation time of the first gas on the second surface is longer than an incubation time of the first gas on the first surface; In (a1), at least a portion of the substance X formed on the substrate is removed; A method for manufacturing a semiconductor device.

19. a first gas supply system that supplies a first gas containing a first element to a substrate having a first surface and a second surface that are made of different materials; a first reactive gas supply system that supplies a first reactive gas that reacts with the substance X containing the first element to the substrate; a control unit configured to be capable of controlling the first gas supply system and the first reactive gas supply system so as to perform a first cycle of non-simultaneously performing (a1) a process of supplying the first gas to the substrate and forming the substance X on at least a portion of the substrate, and (a2) a process of supplying the first reactive gas to the substrate, a first number of times to form a film containing the first element on at least a portion of the substrate, and an incubation time of the first gas on the second surface is made longer than an incubation time on the first surface, and in (a1), a process of removing at least a portion of the substance X formed on the substrate is performed; A substrate processing apparatus comprising:

20. (a1) supplying a first gas containing a first element to a substrate having a first surface and a second surface each made of a different material, to form a material X containing the first element on at least a portion of the substrate; (a2) supplying to the substrate a first reaction gas that reacts with the substance X; a first number of times to form a film containing the first element on at least a portion of the substrate; an incubation time of the first gas on the second surface is longer than an incubation time of the first gas on the first surface; In (a1), at least a portion of the substance X formed on the substrate is removed; A program that causes a computer to execute the procedure in a substrate processing apparatus.

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