Substrate processing method, semiconductor device manufacturing method, substrate processing apparatus and process

Abstract

This invention relates to a substrate processing method, a semiconductor device manufacturing method, a substrate processing apparatus, and a process. The objective is to provide a technique capable of improving the uniformity of a film formed on a substrate surface. The method includes: (a) a process of supplying a first gas to a substrate having a predetermined surface with first adsorption sites, wherein the first gas is a gas that inhibits the adsorption of a second gas on the first adsorption sites; and (b) a process of supplying the second gas to the substrate under conditions where the amount of the second gas adsorbed on the predetermined surface is self-limiting, wherein (a) is started simultaneously with (b) or before (b), and the first gas is adsorbed in a greater amount than the second gas on the predetermined surface.

Description

Substrate processing method, method for manufacturing semiconductor device, substrate processing apparatus, and program The present invention relates to a substrate processing method, a method for manufacturing a semiconductor device, a substrate processing apparatus, and a program. As one step of a substrate processing step (a semiconductor device manufacturing step), a step of forming a film on the surface of a substrate using a reaction-inhibiting gas may be performed (for example, see Patent Document 1). Prior Art Document Patent Document Patent Document 1: Japanese Unexamined Patent Application Publication No. 2022-110465 Problems to be Solved by the Invention The present invention provides a technique capable of improving the uniformity of a film formed on the surface of a substrate. Means for Solving the Problems According to one aspect of the present invention, there is provided a technique having: (a) a step of supplying a first gas to a substrate having a predetermined surface on which a first adsorption site exists, wherein the first gas is a gas that inhibits the adsorption of a second gas to the first adsorption site; and (b) a step of supplying the second gas to the substrate under conditions such that the amount of the second gas adsorbed on the predetermined surface is self-limiting, (a) starting simultaneously with or before (b), and the first gas adsorbing a larger amount than the second gas on the predetermined surface. Effects of the Invention According to the present invention, the uniformity of a film formed on the surface of a substrate can be improved. <One Aspect of the Present Invention> Hereinafter, one aspect of the present invention will be described mainly with reference to FIGS. 1 to 3 and FIGS. 4(a) to 4(c). It should be noted that the drawings used in the following description are all schematic, and the dimensional relationships, ratios of the respective elements shown in the drawings are not necessarily the same as in reality. In addition, the dimensional relationships, ratios of the respective elements are not necessarily the same among the plurality of drawings. (1) Configuration of Substrate Processing Apparatus As shown in FIG. 1, a processing furnace 202 has a heater 207 as a temperature adjustment unit (heating unit). The heater 207 has a cylindrical shape and is vertically installed by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) for activating (exciting) a gas by heat. Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of, for example, quartz (SiO 2) or a heat-resistant material such as silicon carbide (SiC), and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is disposed concentrically with the reaction tube 203. The upper end portion of the manifold 209 is engaged with the lower end portion of the reaction tube 203, and is configured to support the reaction tube 203. An O-ring 220a as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is vertically installed in the same manner as the heater 207. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the cylindrical hollow portion of the processing container. The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed in the processing chamber 201. In the processing chamber 201, nozzles 249a to 249c as the first to third supply portions are respectively provided so as to penetrate the side wall of the manifold 209. The nozzles 249a to 249c are also respectively referred to as the first to third nozzles. The nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC, for example. Gas supply pipes 232a to 232c are respectively connected to the nozzles 249a to 249c. The nozzles 249a to 249c are different nozzles, and the nozzles 249a and 249c are respectively adjacently provided to the nozzle 249b. On the gas supply pipes 232a to 232c, mass flow controllers (MFCs) 241a to 241c as flow controllers (flow control portions) and valves 243a to 243c as on-off valves are respectively provided in order from the upstream side of the gas flow. Gas supply pipes 232d and 232e are respectively connected to the downstream side of the valve 243a of the gas supply pipe 232a. Gas supply pipes 232f and 232g are respectively connected to the downstream sides of the valves 243b and 243c of the gas supply pipes 232b and 232c. MFCs 241d to 241g and valves 243d to 243g are successively provided on the gas supply pipes 232d to 232g from the upstream side of the gas flow. As shown in FIG. 2, the nozzles 249a to 249c are respectively provided in a standing manner in a space that is annular in plan view between the inner wall of the reaction tube 203 and the wafer 200, in the arrangement direction from the lower part to the upper part of the inner wall of the reaction tube 203 toward the wafer 200. The nozzles 249a and 249c are arranged so as to sandwich a straight line L passing through the center of the nozzle 249b and the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer peripheral portion of the wafer 200). The gas supply holes 250a to 250c are respectively opened so as to face the exhaust port 231a in plan view, and can supply gas toward the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203. The first gas is supplied into the processing chamber 201 from the gas supply pipe 232a via the MFC 241a, the valve 243a, and the nozzle 249a.Here, the first gas is a gas that inhibits the adsorption of the second gas and the like and the fourth gas and the like described below onto the wafer 200, or inhibits the adsorption of the second gas and the like and the fourth gas and the like onto the first adsorption site. The third gas is supplied into the processing chamber 201 from the gas supply pipe 232b via the MFC 241b, the valve 243b, and the nozzle 249b. The fourth gas is supplied into the processing chamber 201 from the gas supply pipe 232c via the MFC 241c, the valve 243c, and the nozzle 249c. The second gas is supplied into the processing chamber 201 from the gas supply pipe 232d via the MFC 241d, the valve 243d, the gas supply pipe 232a, and the nozzle 249a. Inert gases are supplied into the processing chamber 201 from the gas supply pipes 232e to 232g via the MFCs 241e to 241g, the valves 243e to 243g, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c. The inert gases function as purifying gases, carrier gases, dilution gases, etc. The first gas supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. The third gas supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. The fourth gas supply system is mainly composed of the gas supply pipe 232c, the MFC 241c, and the valve 243c. The second gas supply system is mainly composed of the gas supply pipe 232d, the MFC 241d, and the valve 243d. The inert gas supply system is mainly composed of the gas supply pipes 232e to 232g, the MFCs 241e to 241g, and the valves 243e to 243g. Any one or all of the above various supply systems may be configured as an integrated supply system 248 integrated with the valves 243a to 243g, the MFCs 241a to 241g, etc. The integrated supply system 248 is configured to be connected to each of the gas supply pipes 232a to 232g, and the supply operations of various substances (various gases) into the gas supply pipes 232a to 232h, that is, the opening and closing operations of the valves 243a to 243g, the flow rate adjustment operations based on the MFCs 241a to 241g, etc. are controlled by a controller 121 described later. The integrated supply system 248 is configured as an integrated unit of an integrated type or a split type, and can be disassembled and assembled with respect to the gas supply pipes 232a to 232g, etc. in units of the integrated unit, and maintenance, replacement, addition, etc. of the integrated supply system 248 can be performed in units of the integrated unit. An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided below the side wall of the reaction tube 203. As shown in FIG. 2, the exhaust port 231a is provided at a position facing (opposite to) the nozzles 249a to 249c (gas supply holes 250a to 250c) with the wafer 200 interposed therebetween in a top view. The exhaust port 231a may also be provided along the lower part to the upper part of the side wall of the reaction tube 203, that is, along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a.On the exhaust pipe 231, a vacuum pump 246 as a vacuum exhaust device is connected via a pressure sensor 245 which is a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 which is a pressure regulator (pressure regulation unit). The APC valve 244 can perform vacuum exhaust and stop of vacuum exhaust in the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating. The APC valve 244 is further configured to adjust the valve opening based on the pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating, thereby being able to adjust the pressure in the processing chamber 201. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. It is also possible to consider including the vacuum pump 246 in the exhaust system. A seal cover 219 as a furnace port cover body that can airtightly seal the lower end opening of the manifold 209 is provided below the manifold 209. An O-ring 220b as a sealing member that abuts against the lower end of the manifold 209 is provided on the upper surface of the seal cover 219. A rotation mechanism 267 that rotates a susceptor 217 described later is provided below the seal cover 219. The rotation shaft 255 of the rotation mechanism 267 penetrates the seal cover 219 and is connected to the susceptor 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the susceptor 217. The seal cover 219 is configured to move up and down in the vertical direction by a susceptor elevator 115 which is a lifting mechanism provided outside the reaction tube 203. The susceptor elevator 115 is a transfer device (transfer mechanism) configured to transfer (load and unload) the wafer 200 into and out of the processing chamber 201 by moving the seal cover 219 up and down. A gate 219s as a furnace port cover body is provided below the manifold 209, and it can airtightly seal the lower end opening of the manifold 209 in a state where the seal cover 219 is lowered and the susceptor 217 is unloaded from the processing chamber 201. An O-ring 220c as a sealing member that abuts against the lower end of the manifold 209 is provided on the upper surface of the gate 219s. The opening and closing operation (lifting operation, rotation operation, etc.) of the gate 219s is controlled by a gate opening and closing mechanism 115s. The susceptor 217 as a substrate support member is configured to support a plurality of, for example, 25 to 200 wafers 200 in a horizontal posture and arranged in a multi-layered state with their centers aligned with each other along the vertical direction, even if they are arranged at intervals. The susceptor 217 is made of a heat-resistant material such as quartz or SiC, for example. Below the susceptor 217, a heat insulating plate 218 made of a heat-resistant material such as quartz or SiC is supported in multiple layers. It should be noted that the expression of the numerical range "25 to 200" in this specification means that the lower limit value and the upper limit value are included in this range. Therefore, for example, "25 to 200" means "25 or more and 200 or less". The same applies to other numerical ranges.A temperature sensor 263, which serves as a temperature detector, is provided 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 inside the processing chamber 201 is made to have a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203. As shown in FIG. 3, the controller 121, which serves as a control unit (control means), is configured as a computer including a CPU (Central Processing Unit; central processing unit) 121a, a RAM (Random Access Memory; random access memory) 121b, a memory device 121c, and an I / O port 121d. The RAM 121b, the memory 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, which is configured as a touch panel or the like, is connected to the controller 121. In addition, an external memory device 123 can be connected to the controller 121. It should be noted that the substrate processing apparatus can be configured to have one control unit or multiple control units. That is, the control of the processing sequence described below can be performed using one control unit, or the control of the processing sequence described below can be performed using multiple control units. In addition, the multiple control units can be configured as a control system connected to each other via a wired or wireless communication network, or the control of the processing sequence described below can be performed by the entire control system. When the term "control unit" is used in this specification, in addition to the case including one control unit, there is also a case including multiple control units and a case including a control system composed of multiple control units. The memory device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive; hard disk drive), an SSD (Solid State Drive; solid state drive), or the like. A control program for controlling the operation of the substrate processing apparatus, a process recipe, which describes the sequence, conditions, etc. of the substrate processing described below, are recorded and stored in the memory device 121c in a readable manner. The process recipe is combined in such a way that the substrate processing apparatus executes each sequence of the substrate processing described below through the controller 121 and can obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are collectively abbreviated as programs. In addition, the process recipe is also abbreviated as a recipe. When the term "program" is used in this specification, it sometimes includes only the recipe alone, sometimes includes only the control program alone, or sometimes includes both. The RAM 121b is configured as a memory area (working area) that temporarily holds programs, data, etc. read by the CPU 121a.The I / O port 121d is connected to the aforementioned MFCs 241a - 241g, valves 243a - 243g, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, susceptor elevator 115, gate opening / closing mechanism 115s, etc. The CPU 121a is configured to be able to read a control program from the memory device 121c and execute it, and read a recipe from the memory device 121c based on the input of an operation command from the input / output device 122, etc. The CPU 121a is configured to be able to perform flow rate adjustment operations of various substances (various gases) based on the MFCs 241a - 241g, opening / closing operations of the valves 243a - 243g, opening / closing operations of the APC valve 244, pressure adjustment operations using the APC valve 244 based on the pressure sensor 245, start and stop of the vacuum pump 246, temperature adjustment operations of the heater 207 based on the temperature sensor 263, rotation and rotation speed adjustment operations of the susceptor 217 based on the rotation mechanism 267, lifting operations of the susceptor 217 based on the susceptor elevator 115, opening / closing operations of the gate 219s based on the gate opening / closing mechanism 115s, etc. according to the content of the read recipe. The controller 121 can be constituted by installing the above program recorded and stored in the external memory device 123 into the computer. The external memory device 123 includes, for example, magnetic disks such as HDDs, optical disks such as CDs, magneto-optical disks such as MOs, USB memories, semiconductor memories such as SSDs, etc. The memory device 121c and the external memory device 123 are configured as computer-readable recording media. Hereinafter, they are collectively and simply referred to as recording media. When using the term recording media in this specification, sometimes it only includes the memory device 121c alone, sometimes it only includes the external memory device 123 alone, or sometimes it includes both. Additionally, instead of using the external memory device 123, communication means such as the Internet or dedicated lines can be used to provide the program to the computer. (2) Substrate processing process A method for processing a substrate in one process of the manufacturing process of a semiconductor device using the above-described substrate processing apparatus, that is, an example of the processing sequence for forming a film on a wafer 200 as the substrate, will be mainly described with reference to FIG. 4. In the following description, the operations of each part constituting the substrate processing apparatus are controlled by the controller 121. In the processing sequence of this mode, there are: (a) a step of supplying a first gas to the wafer 200 having a predetermined surface with a first adsorption site, where the first gas is a gas that inhibits the adsorption of a second gas to the first adsorption site; and (b) a step of supplying the second gas to the wafer 200 under the condition that the amount of the second gas adsorbed on the predetermined surface becomes self-limiting, where (a) starts simultaneously with or before (b), and the first gas has a larger adsorption amount on the predetermined surface than the second gas.In addition, the following describes the following situation: further having the step of forming a first adsorption site on at least a part of a predetermined surface, and performing the first cycle that performs (c) after (a) and (b) a predetermined number of times (n times, where n is an integer of 1 or more). In addition, the following describes the case where a third gas is supplied to the wafer 200 in (c) to form a first adsorption site on at least a part of the predetermined surface. The following describes the case where the first gas contains a first element, the second gas contains a second element, and the third gas contains a third element. In this specification, for convenience, the above processing sequence is sometimes expressed in the following manner. The same expression is also used in the description of the following modification examples, other methods, etc. (First gas → Purification → Second gas → Purification → Third gas → Purification) × n. The term "wafer" used in this specification may refer to the wafer itself or a laminate of the wafer and a predetermined layer or film formed on its surface. The term "surface of the wafer" used in this specification may refer to the surface of the wafer itself or the surface of a predetermined layer formed on the wafer. When it is described in this specification that "a predetermined layer is formed on the wafer", it may refer to the case where the predetermined layer is directly formed on the surface of the wafer itself, or the case where the predetermined layer is formed on a layer formed on the wafer. The use of "substrate" in this specification is also synonymous with the use of "wafer". The term "agent" used in this specification includes at least any one of gaseous substances and liquid substances. Liquid substances include aerosol substances. That is, each of the first raw material, the second raw material, and the oxidant may contain a gaseous substance, a liquid substance such as an aerosol substance, or both. The term "layer" used in this specification includes at least any one of continuous layers and discontinuous layers. For example, the first layer 300 and the second layer 400 described later may include a continuous layer, a discontinuous layer, or both. In this specification, when describing the adsorption and reaction of the first gas, the second gas, the third gas, and the fourth gas on the surface of the wafer 200 respectively, it includes not only the manner in which they adsorb and react on the wafer surface in an undecomposed state, but also the manner in which intermediates generated by their decomposition and the detachment of their ligands adsorb and react on the surface of the wafer 200. (Wafer filling and susceptor loading) When a plurality of wafers 200 are loaded (wafer filling) into the susceptor 217, the gate 219s is moved by the gate opening / closing mechanism 115s, and the lower end opening of the manifold 209 is opened (gate opening). After that, as shown in FIG. 1, the susceptor 217 supporting a plurality of wafers 200 is lifted by the susceptor elevator 115 and carried into the processing chamber 201 (susceptor loading). In this state, the seal cover 219 is in a state of sealing the lower end of the manifold 209 via the O-ring 220b. In this way, the wafers 200 are prepared (provided) in the processing chamber 201.It should be noted that the wafer 200 filled in the susceptor 217 has a predetermined surface with a first adsorption site. In this embodiment, as an example, the case where the first adsorption site exists on the predetermined surface of the wafer 200 will be described. It should be noted that the wafer 200 may also have a surface that exposes a substance different from the substance constituting the predetermined surface. (Pressure adjustment and temperature adjustment) After the susceptor loading is completed, vacuum evacuation (pressure reduction evacuation) is performed by the vacuum pump 246 so that the inside of the processing chamber 201, that is, the space where the wafer 200 is located, becomes a desired pressure (vacuum degree). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and feedback control is performed on the APC valve 244 based on the measured pressure information. In addition, the wafer 200 inside the processing chamber 201 is heated by the heater 207 to make it a desired processing temperature. At this time, feedback control is performed on the energization state of the heater 207 based on the temperature information detected by the temperature sensor 263 so that a desired temperature distribution is formed inside the processing chamber 201. In addition, the rotation of the wafer 200 is started by the rotation mechanism 267. The evacuation inside the processing chamber 201, the heating of the wafer 200, and the rotation are continuously performed at least until the processing of the wafer 200 is completed. (Film formation process) After that, the following steps A, B, and C are sequentially executed. [Step A] In this step, a first gas is supplied to the wafer 200 inside the processing chamber 201. Specifically, the valve 243a is opened to allow the first gas to flow into the gas supply pipe 232a. The first gas is flow-regulated by the MFC 241a, supplied into the processing chamber 201 via the nozzle 249a, and discharged from the exhaust port 231a. At this time, the first gas is supplied to the wafer 200 from the side of the wafer 200 (first gas supply). At this time, the valves 243e to 243g may be opened to supply inert gases into the processing chamber 201 via the nozzles 249a to 249c, respectively. As the processing conditions when the first gas is supplied in this step, the following can be exemplified: Processing temperature: 350 to 700 °C, preferably 500 to 600 °C Processing pressure: 1 to 10000 Pa, preferably 10 to 1333 Pa First gas supply flow rate: 0.01 to 3 slm, preferably 0.1 to 1 slm First gas supply time: 10 to 120 seconds, preferably 20 to 60 seconds Inert gas supply flow rate (for each gas supply pipe): 0 to 10 slm. 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, that is, the pressure of the space where the wafer 200 is located. In addition, when the supply flow rate includes 0 slm, 0 slm means that the gas (substance) is not supplied. The same applies to the following descriptions.By supplying the first gas to the wafer 200 under the above processing conditions, at least one of the first gas, a substance having a part of the molecular structure of the first gas, and the first element contained in the first gas can be adsorbed to the first adsorption sites existing on the surface of the wafer 200 (see (a) in FIG. 4). Hereinafter, at least one of the first gas, a substance having a part of the molecular structure of the first gas, and the first element contained in the first gas may be referred to as the first gas, etc. It should be noted that in (a) to (c) in FIG. 4, the first gas, etc. are represented by the letter α. For reasons described later, this step is preferably carried out under conditions such that the amount (adsorption amount) of the first gas adsorbed on the surface of the wafer 200 becomes self-limiting and the amount of the first gas adsorbed on the surface of the wafer 200 becomes unsaturated. In this specification, the condition that the adsorption amount of a gas becomes self-limiting is synonymous with the condition that the adsorption amount of the gas becomes self-limiting or the condition that the adsorption amount of the gas asymptotically approaches a certain value. Specifically, it refers to a condition where it is considered that as the supply time of the gas is extended, the adsorption amount of the gas reaches a certain amount and tends to saturate. The so-called considering that the adsorption amount of the gas reaches a certain amount and tends to saturate includes not only the case where the adsorption amount of the gas is actually saturated, but also the concept of the case where saturation does not actually occur but will occur (in the future) as time passes. In addition, the condition that the amount (adsorption amount) of the first gas adsorbed on the surface of the wafer 200 becomes unsaturated specifically refers to a condition where the first gas is not adsorbed at all the first adsorption sites on the surface of the wafer 200, but only the first adsorption sites for adsorbing the second gas supplied in step B described later remain. As the inert gas, nitrogen gas (N can be used. 2) Rare gases such as argon gas (Ar), helium gas (He), neon gas (Ne), and xenon gas (Xe). As inert gases, one or more of them can be used. The same applies to each of the steps described below. After the first gas is adsorbed on the surface of the wafer 200, the valve 243a is closed to stop the supply of the first gas into the processing chamber 201. Then, the inside of the processing chamber 201 is evacuated to remove gaseous substances and the like remaining in the processing chamber 201 from the processing chamber 201. At this time, the valves 243e to 243g are opened, and an inert gas is supplied into the processing chamber 201 via the nozzles 249a to 249c. The inert gas supplied from the nozzles 249a to 249c acts as a purge gas, whereby the space where the wafer 200 exists, that is, the inside of the processing chamber 201, is purged. [Step B] After Step A is completed, a second gas is supplied to the wafer 200 inside the processing chamber 201, that is, the wafer 200 after the first gas is adsorbed on its surface. Specifically, the valve 243d is opened to allow the second gas to flow into the gas supply pipe 232d. The second gas is flow-controlled by the MFC241d and supplied into the processing chamber 201 via the nozzle 249a, and exhausted from the exhaust port 231a. At this time, the second gas is supplied to the wafer 200 from the side of the wafer 200 (second gas supply). At this time, the valves 243e to 243g can also be opened to supply an inert gas into the processing chamber 201 via the nozzles 249a to 249c, respectively. Examples of the processing conditions when the second gas is supplied in this step include: Processing temperature: 20 to 700 °C, preferably 200 to 600 °C, more preferably 500 to 600 °C Processing pressure: 1 to 10000 Pa, preferably 10 to 2666 Pa, more preferably 1000 to 2666 Pa Second gas supply flow rate: 0.01 to 4 slm, preferably 0.3 to 1 slm Second gas supply time: 1 to 360 seconds, preferably 5 to 180 seconds. Other processing conditions can be set to be the same as those when the first gas is supplied in Step A. However, this step is performed under conditions that make the adsorption amount of the second gas adsorbed on the surface of the wafer 200 having the first adsorption site self-limiting. By supplying the second gas to the wafer 200 under the above processing conditions, at least one of the second gas, a substance having a part of the molecular structure of the second gas, and the second element contained in the second gas can be adsorbed on the portion of the surface of the wafer 200 where the first gas is not adsorbed, that is, the remaining first adsorption sites on the surface of the wafer 200. Thereby, a first layer 300 having the first element and the second element can be formed on the surface of the wafer 200 (see (b) in FIG. 4). Hereinafter, at least one of the second gas, a substance having a part of the molecular structure of the second gas, and the second element contained in the second gas may sometimes be referred to as the second gas and the like.It should be noted that in (b) of FIG. 4 and (c) of FIG. 4, the second gas etc. are represented by the character β. Here, the first gas is a gas that inhibits the adsorption of the second gas on the first adsorption site. Therefore, as shown in (b) of FIG. 4, the second gas etc. do not adsorb on the first gas etc. on the surface of the wafer 200. Here, in this specification, the so-called "the second gas etc. do not adsorb on the first gas etc." not only includes the case where the second gas etc. do not adsorb on the first gas etc. at all, but also includes the case where an extremely small amount of the second gas etc. adsorb on the first gas etc. For example, it also includes the case where the second gas etc. adsorb on about 1% of the first gas etc. among the first gas etc. on the wafer 200, preferably adsorb on the first gas etc. below 1%. By performing step A and step B, the first gas etc. and the second gas etc. can be adsorbed at the first adsorption site provided on the surface of the wafer 200, and the first layer 300 including the first element and the second element is formed (see (b) of FIG. 4). In other words, a first layer doped with the second element can be formed. A predetermined adsorption site for the third gas to be supplied in the subsequent step C is formed on the surface of the first layer 300. By performing step A and step B under the above processing conditions, the adsorption amount of the first gas on the surface of the wafer 200 can be made more than the adsorption amount of the second gas on the surface of the wafer 200. It can be carried out under the condition that the adsorption amount of the second gas on the wafer 200 is not saturated. This step (step B) can be carried out under the condition that the adsorption amount of the second gas on the surface of the wafer 200 is not saturated, or can also be carried out under the saturated condition. It should be noted that the condition that the adsorption amount of the second gas on the surface of the wafer 200 is not saturated specifically means the condition that all the adsorption sites remaining on the surface of the wafer 200 do not adsorb the second gas. After the first layer 300 is formed on the surface of the wafer 200, the valve 243d is closed, and the supply of the second gas into the processing chamber 201 is stopped. Then, the inside of the processing chamber 201 is evacuated, and the gaseous substances etc. remaining in the processing chamber 201 are exhausted from the processing chamber 201. At this time, the valves 243e to 243g are opened, and an inert gas is supplied into the processing chamber 201 via the nozzles 249a to 249c. The inert gas supplied from the nozzles 249a to 249c functions as a purge gas, whereby the space where the wafer 200 exists, that is, the inside of the processing chamber 201 is purged. [Step C] After step B is completed, the third gas is supplied to the wafer 200 in the processing chamber 201, that is, the wafer 200 having the first layer 300 formed on its surface. Specifically, the valve 243b is opened, and the third gas flows into the gas supply pipe 232b. The flow rate of the third gas is adjusted by the MFC241b, and it is supplied into the processing chamber 201 via the nozzle 249b, and exhausted from the exhaust port 231a. At this time, the third gas is supplied to the wafer 200 from the side of the wafer 200 (third gas supply).At this time, valves 243e to 243g can also be opened to supply inert gas into the processing chamber 201 through nozzles 249a to 249c respectively. As the processing conditions when supplying the third gas in this step, the following can be exemplified: Processing temperature: 20 to 700 °C, preferably 200 to 600 °C, more preferably 500 to 600 °C; Processing pressure: 100 to 10,000 Pa, preferably 1000 to 10,000 Pa; Third gas supply flow rate: 0.1 to 20 slm, preferably 1 to 10 slm; Third gas supply time: 1 to 120 seconds, preferably 3 to 15 seconds. Other processing conditions can be set to be the same as those when supplying the first gas in step A. By supplying the third gas to the wafer 200 under the above processing conditions, the third gas and / or the third element contained in the third gas can be adsorbed on at least a part of the first layer 300 formed on the surface of the wafer 200 (see (c) in FIG. 4). It should be noted that in (c) of FIG. 4, the third gas and / or the third element contained in the third gas are represented by the letter γ. Hereinafter, the third gas and / or the third element contained in the third gas may sometimes be referred to as the third gas, etc. By supplying the third gas to the wafer 200 under the above processing conditions, at least a part of the first layer 300 formed on the surface of the wafer 200 reacts with the third gas and is modified. As a result, a second layer 400, which is a modified layer of the first layer 300 and has the first adsorption sites, is formed on at least a part of the surface of the wafer 200 (see (c) in FIG. 4). The first adsorption sites formed in this step function as adsorption sites for the first gas and the second gas supplied in step A and step B of the next cycle. After the second layer 400 is formed on the surface of the wafer 200, valve 243b is closed to stop the supply of the third gas into the processing chamber 201. Then, the inside of the processing chamber 201 is evacuated to remove gaseous substances and the like remaining in the processing chamber 201 from the processing chamber 201. At this time, valves 243e to 243g are opened to supply inert gas into the processing chamber 201 through nozzles 249a to 249c. The inert gas supplied from nozzles 249a to 249c functions as a purge gas, whereby the space where the wafer 200 is located, that is, the inside of the processing chamber 201, is purged. [Scheduled number of executions] By performing the first cycle of steps A to C above non-simultaneously, that is, sequentially, n times (n is an integer of 1 or more), a predetermined film is formed on the surface of the wafer 200. The above first cycle is preferably repeated multiple times. That is, it is preferable that the thickness of the second layer 400 formed in each cycle is thinner than the desired film thickness, and the above first cycle is repeated multiple times until the thickness of the predetermined film formed by stacking the second layer 400 becomes the desired thickness.In this method, it can also be regarded that the first gas supplied in step A is used as an adsorption inhibitor to inhibit the raw materials of the above-mentioned predetermined film and the second gas supplied in step B from being adsorbed onto the first adsorption sites and the surface of the wafer 200. It can also be regarded that the second gas supplied in step B is used as a doping agent gas for forming the above-mentioned predetermined film doped with the second element. It can also be regarded that the third gas supplied in step C is used as a modifier for modifying the first layer 300 formed by performing steps A and B into the second layer 400. (Post-purification and atmospheric pressure recovery) After the film formation process is completed, an inert gas as a purification gas is supplied into the processing chamber 201 from each of the nozzles 249a to 249c, and exhaust is performed from the exhaust port 231a. Thus, the inside of the processing chamber 201 is purified, and the gas, reaction by-products, etc. remaining in the processing chamber 201 are removed from the processing chamber 201 (post-purification). Then, the atmosphere inside the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure inside the processing chamber 201 is restored to normal pressure (atmospheric pressure recovery). (Cassette unloading and wafer removal) After that, the sealing lid 219 is lowered by the cassette elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafer 200 is carried out (cassette unloading) from the lower end of the manifold 209 in a state of being supported by the cassette 217 to the outside of the reaction tube 203. After the cassette unloading, the gate 219s is moved, and the lower end opening of the manifold 209 is sealed by the gate 219s via the O-ring 220c (gate closing). After the processed wafer 200 is carried out to the outside of the reaction tube 203, it is taken out from the cassette 217 (wafer removal). (3) Effects of this method According to this method, in addition to the above effects, one or more of the following effects can also be obtained. (a) After supplying the first gas in step A, the second gas is supplied in step B, so that the adsorption amount of the first gas on the surface of the wafer 200 is more than the adsorption amount of the second gas. Thus, even when the adsorption amount of the second gas is small relative to the number of the first adsorption sites at the start of step A, the controllability of the adsorption amount of the second gas and the uniformity of the adsorption amount of the second gas on the surface of the wafer 200 can be improved. In addition, in step B, by supplying the second gas under the condition that the adsorption amount of the second gas adsorbed on the surface of the wafer 200 is self-limiting, the controllability of the adsorption amount of the second gas can be improved. Hereinafter, an explanation will be given. When the second gas is adsorbed on the first adsorption sites existing on the surface of the wafer 200, there is a tendency that the difference between the part with a large adsorption amount of the second gas and the part with a small adsorption amount of the second gas becomes larger as the adsorption amount of the second gas is to be reduced more relative to the number of the first adsorption sites. That is, the deviation of the adsorption amount of the second gas on the surface of the wafer 200 becomes larger. Therefore, the uniformity of the adsorption amount of the second gas on the surface of the wafer 200 and the controllability of the adsorption amount of the second gas are likely to decrease.In this method, after supplying the first gas in step A, the second gas is supplied in step B. Furthermore, the adsorption amount of the first gas on the surface of the wafer 200 is made larger than that of the second gas. That is, before starting step B, the first gas is adsorbed on a relatively large number of the first adsorption sites among the plurality of first adsorption sites existing on the surface of the wafer 200. Thus, at the start of step B, the number of the first adsorption sites capable of adsorbing the second gas becomes smaller, and therefore the deviation of the adsorption amount of the second gas on the surface of the wafer 200 can be reduced. In addition, the first gas is a gas that inhibits the second gas from adsorbing to the first adsorption sites or a predetermined surface. Thus, the second gas becomes less likely to adsorb on the first gas or the like that has already been adsorbed on the surface of the wafer 200. From the above, it can be seen that the second gas becomes more likely to preferentially adsorb to the first adsorption sites on the surface of the wafer 200 where the first gas or the like is not adsorbed. Therefore, in step B, the adsorption amount of the second gas on the surface of the wafer 200 can be made less likely to exceed the desired amount. As a result, the uniformity of the adsorption amount of the second gas on the surface of the wafer 200 can be improved. In addition, in this method, in step B, the second gas is supplied under the condition that the adsorption amount of the second gas adsorbed on the surface of the wafer 200 is self-limiting. That is, the second gas is supplied under the condition that it can be regarded that as the supply time of the second gas is extended, the adsorption amount of the second gas adsorbed on the surface of the wafer 200 reaches saturation at a certain amount. Thus, in step B, the adsorption amount of the second gas on the surface of the wafer 200 can be made less likely to exceed the desired amount. As a result, the controllability of the adsorption amount of the second gas can be improved. It should be noted that for the tendency that the difference between the part with a large adsorption amount and the part with a small adsorption amount of the second gas becomes larger in the case where the second gas is adsorbed on the first adsorption sites, it becomes significant when the second gas is supplied from the side of the wafer 200 in step B. The technology of the present invention can improve the controllability of the adsorption amount of the second gas and the uniformity of the adsorption amount of the second gas on the surface of the wafer 200 even when the second gas is supplied from the side of the wafer 200. (b) Step A is carried out under the condition that the amount (adsorption amount) of the first gas adsorbed on the surface of the wafer 200 becomes self-limiting and the amount of the first gas adsorbed on the surface of the wafer 200 becomes unsaturated. Thus, in step A, it becomes easy to control the number of the first adsorption sites where the first gas is not adsorbed. As a result, the controllability of the adsorption amount of the second gas adsorbed on the predetermined surface can be improved. (c) By carrying out step B under the condition that the amount of the second gas adsorbed on the surface of the wafer 200 becomes unsaturated, compared with the case where step B is carried out under the condition that the adsorption amount of the second gas reaches saturation, step B can be carried out in a shorter time. Thus, the productivity can be improved. (d) By carrying out step A and step B, the first layer 300 can be formed on the surface of the wafer 200.More specifically, by performing Step A and Step B, the first layer 300 containing the first element and the second element can be uniformly formed on the surface of the wafer 200. In addition, the controllability of the amount of the second element contained in the first layer 300 can be improved. (e) By making the second element different from the first element, the first layer 300 containing the second element can be uniformly formed on the surface of the wafer 200. In addition, the controllability of the amount of the second element contained in the first layer 300 can be improved. (f) By performing Step C, the second layer 400 can be formed on the surface of the wafer 200. More specifically, by performing Step C, a film can be formed in which the amount of the second element contained is sufficiently controlled and which contains the first element, the second element, and the third element. In other words, a sufficiently controlled amount of the second element can be added to a film mainly composed of the first element and the third element. Here, as the first element, for example, one or more of tungsten (W), titanium (Ti), molybdenum (Mo), tantalum (Ta), cobalt (Co), yttrium (Y), ruthenium (Ru), hafnium (Hf), zirconium (Zr), aluminum (Al), silicon (Si), boron (B), gallium (Ga), indium (In), phosphorus (P), carbon (C), etc. can be used. For example, as the third gas, a gas containing a reducing gas, an oxidizing gas, a nitriding gas, a sulfiding gas, a selenizing gas, a tellurizing gas, etc. can be used. One or more of them can be used as the third gas. For example, when the third gas is a reducing gas, a film composed of the first element and the second element can be formed on the wafer 200. For example, when the third gas is any one of an oxidizing gas, a nitriding gas, a sulfiding gas, a selenizing gas, a tellurizing gas, an oxide film containing the first element and the second element, a nitride film containing the first element and the second element, a sulfide film containing the first element and the second element, a selenide film containing the first element and the second element, a telluride film containing the first element and the second element can be formed on the wafer 200. As the first gas, for example, a gas containing the first element and a halogen element as described above can be used. As such a gas, for example, tungsten hexachloride (WCl 6 ), tungsten hexafluoride (WF 6 ), titanium tetrachloride (TiCl 4 ), titanium tetrafluoride (TiF 4 ), molybdenum pentachloride (MoCl 5 ), molybdenum pentafluoride (MoF 5 ), molybdenum dichloride dioxide (MoO 2 Cl 2) Molybdenum oxychloride (MoOCl 4 ) Tantalum pentachloride (TaCl 5 ) Tantalum pentafluoride (TaF 5 ) Cobalt difluoride (CoF 2 ) Cobalt dichloride (CoCl 2 ) Yttrium trifluoride (YF 3 ) Yttrium trichloride (YCl 3 ) Ruthenium trichloride (RuCl 3 ) Ruthenium trifluoride (RuF 3 ) Hafnium tetrachloride (HfCl 4 ) Hafnium tetrafluoride (HfF 4 ) Zirconium tetrachloride (ZrCl 4 ) Zirconium tetrafluoride (ZrF 4 ) Aluminum trichloride (AlCl 3 ) Aluminum trifluoride (AlF 3 ) Dichlorosilane (SiH 2 Cl 2 ) 1,2-Dichlorosilane (Si 2 H 4 Cl 2 ) 1,1,1-Trichloroethylsilane (Si 2 H 3 Cl 3 ) 1,1,2-Trichloroethylsilane (Si 2 H 3 Cl 3 ) Pentachlorodisilane (Si 2 HCl 5 )), hexachlorodisilane (Si 2 Cl 6 ), tetrafluorosilane (SiF 4 ), and so on. Additionally, as the first gas, for example, silane (SiH 4 ), disilane (Si 2 H 6 ), trisilane (Si 3 H 8 ), tetrasilane (Si 4 H 10 ), boron trifluoride (BF 3 ), boron trichloride (BCl 3 ), gallium trifluoride (GaF 3 ), gallium trichloride (GaCl 3 ), indium trifluoride (InF 3 ), indium trichloride (InCl 3 ), phosphorus trifluoride (PF 3 ), phosphorus pentafluoride (PF 5 ), phosphorus trichloride (PCl 3 ), phosphorus pentachloride (PCl 5 ), carbon tetrafluoride (CF 4 ), carbon tetrachloride (CCl 4 ), trifluoromethane (CHF 3 ), fluoromethane (CH 3 F), trichloromethane (CHCl 3 ), chloromethane (CH 3Cl), etc. In addition, as the first gas, for example, a gas having the first element and the organic ligand as described above, or a gas having the first element and the hydrogen group as described above can be used. As such a gas, for example, the following can be used: hexakis(dimethylamino)ditungsten (W 2 [N(CH 3 ) 2 6 ), bis(tert-butylamido)bis(dimethylamido)tungsten ((t-C 4 H 9 NH) 2 W=(Nt-C 4 H 9 ) 2 ), tetraethyl(methylamido)titanium (Ti[N(C 2 H 5 )(CH 3 )] 4 ), bis(ethylcyclopentadienyl)ruthenium (Ru(CH 2 CH 3 )Cp) 2 ), bis(cyclopentadienyl)ruthenium (Ru(Cp) 2 ), tetraethyl(methylamido)hafnium (Hf[N(CH 3 )(CH 2 CH 3 )] 4 ), tetra(diethylamido)hafnium (Hf[N(CH 2 CH 3 ) 2 4 ), tetra(dimethylamido)hafnium (Hf[N(CH 3 ) 2 4 ) tris(dimethylamino)cyclopentadienylhafnium ((Cp)Hf[N(CH 3 ) 2 3 ) tetramethylethylaminozirconium (Zr[N(CH 3 )Cp] 4 ) tetrakis(diethylamino)zirconium (Zr[N(CH 2 CH 3 ) 2 4 ) tetrakis(dimethylamino)zirconium (Zr[N(CH 3 ) 2 4 ) tris(dimethylamino)cyclopentadienylzirconium ((Cp)Zr[N(CH 3 ) 2 3 ) trimethylaluminum (Al(CH 3 ) 3 ) tris(dimethylamino)silane (Si[N(CH 3 ) 2 3 H) borane (BH 3 ) trimethylgallium (Ga(CH 3 ) 3 ) trimethylindium (In(CH 3 ) 3 ) phosphine (PH 3 ) methane (CH 4 ) etc. Here, as the second element, for example, one or more of the elements cited as examples of the first element can be used. Further, as the second gas, for example, one or more of the gases containing one or more of the gases cited as examples of the first gas can be used. As the reducing gas, for example, it is possible to use: containing hydrogen (H 2 ) gas, deuterium (D 2 ) gas, borane (BH 3 ) gas, diborane (B 2 H 6 ) gas, carbon monoxide (CO) gas, ammonia (NH 3 ) gas, silane (SiH 4 ) gas, disilane (Si 2 H 6 ) gas, trisilane (Si 3 H 8 ) gas, germane (GeH 4 ) gas, digermane (Ge 2 H 6 ) etc. one or more of the gases. Further, as the reaction gas, for example, an oxidizing gas containing oxygen (O) gas can be used. As the oxidizing gas, for example, it is possible to use: containing oxygen (O 2 ), ozone (O 3 ), water vapor (H 2 O), H 2 and O 2 of the mixed gas, hydrogen peroxide (H 2 O 2 ), nitrous oxide (N 2 O) etc. one or more of the gases. As the nitriding gas, for example, it is possible to use: ammonia (NH 3) Gas, diazene (N 2 H 2 ) Gas, hydrazine (N 2 H 4 ) Gas, N 3 H 8 One or more of hydrogen nitride-based gases such as gas. As the sulfur-containing gas, for example, those containing hydrogen sulfide (H 2 S), disulfane (H 2 S 2 ), ammonium disulfide ((NH 4 ) 2 S), dimethyl sulfide ((CH 3 ) 2 S) and the like can be used. As the sulfur-containing gas, one or more of them can be used. As the selenium-containing gas, for example, those containing hydrogen selenide (H 2 Se), hydrogen diselenide (H 2 Se 2 ), dimethyl selenide ((CH 3 ) 2 Se) and the like can be used. As the selenium-containing gas, one or more of them can be used. As the tellurium-containing gas, for example, those containing hydrogen telluride (H 2 Te), hydrogen ditelluride (H 2 Te 2 ), dimethyl telluride ((CH 3 ) 2Gases such as Te). As the tellurium-containing gas, one or more of them can be used. (4) Modification Examples The substrate processing sequence in this embodiment can be changed as in the following modification examples. These modification examples can be arbitrarily combined. Unless otherwise specified, the processing sequence and processing conditions in each step of each modification example can be set to be the same as those in each step of the above-described substrate processing sequence. Hereinafter, in the configuration of the layer (film) formed on the surface of the wafer 200 described with reference to FIGS. 5(a) to 6(c), only the elements different from the layer formed on the surface of the wafer 200 described with reference to FIGS. 4(a) to 4(c) are described, and the substantially same elements are denoted by the same reference numerals and their description is omitted. (Modification Example 1) As in the following processing sequence, the first cycle of performing step C can be performed a predetermined number of times (n 1 times, n 1 is an integer of 1 or more), and further, the second cycle can be performed a predetermined number of times (n 2 times, n 2 is an integer of 1 or more), and the cycle in which the second cycle is sequentially performing step A and step C can be performed a predetermined number of times (n 3 times, n 3 is an integer of 1 or more), where the second cycle is a cycle of sequentially performing step A and step C. {(First gas → Purification → Second gas → Purification → Third gas → Purification) × n 1 → (First gas → Purification → Third gas → Purification) × n 2} × n 3As an example, FIG. 5 shows a layer (film) formed by performing the first cycle and the second cycle each once for a total of two times. In FIG. 5, the first cycle is represented by the letter X, and the second cycle is represented by the letter Y. Additionally, in FIG. 5, the layer (the second layer) formed by performing the first cycle is labeled with the symbol 400, and the layer formed by performing the second cycle is labeled with the symbol 500. In this modified example, the same effect or a part of the effect as in the above-described method can also be obtained. Further, in this modified example, in addition to the second layer 400 containing the second element, a layer 500 not containing the second element is also formed, whereby a film with a lower content of the second element can be formed. For example, if the number of times the second cycle is performed is increased relative to the number of times the first cycle is performed, a film with a lower content of the second element than in the above-described method can be formed. It should be noted that in FIG. 5, as an example, it is shown that the first adsorption sites are formed on the entire surface of the second layer 400 in step C, but it is not limited thereto, and the first adsorption sites may be formed only on a part of the surface of the second layer 400. In this case, the same effect as in the above-described method can also be obtained. In this case, in step C, since the first adsorption sites are formed only on a part of the surface of the second layer 400, the number of the first adsorption sites on the surface of the second layer 400 can be reduced. As a result, in the next cycle, the first layer 300 with a lower content of the second element can be formed. Consequently, a film with a lower content of the second element can be formed. (Modified Example 2) It is also possible to perform the cycle of step D a predetermined number of times (m 1 times, m 1 is an integer of 1 or more) after performing steps A and B, and in this step D, at least a part of the first gas adsorbed on the surface of the wafer 200 is removed. (First gas → Purification → Second gas → Purification → Removal of the first gas → Purification) × m 1By performing Step A and Step B, the first gas, etc. and the second gas, etc. are adsorbed on the surface of the wafer 200 to form the first layer 300 (see (a) in FIG. 6). Then, by performing Step D, at least a part of the first gas adsorbed on the surface of the wafer 200 is removed (see (b) in FIG. 6). As Step D, for example, a step of removing the first gas from the wafer 200 can be performed. Examples of the removal of the first gas include heating the wafer 200 to a temperature at which the first gas desorbs from the wafer 200; or supplying a removing agent (for example, one or more of a reducing gas, an oxidizing gas, and a nitriding gas described later) to the wafer 200. Here, as the processing conditions when supplying the removing agent in this step, the processing conditions when supplying the third gas in Step C can be used. In addition, as in the following processing sequence, after performing Step A, Step B, and Step D, the cycle of performing Step E can be further repeated a predetermined number of times (m 2 times, m 2 is an integer of 1 or 2 or more), and in this Step E, a fourth gas having a fourth element and different from the first gas is supplied. (First gas → Purification → Second gas → Purification → Removal of first gas → Purification → Fourth gas → Purification) × m 2Here, in this modification example, as the fourth element, for example, one or more of the elements exemplified as examples of the first element can be used. Further, as the fourth gas, for example, a gas containing one or more of the gases exemplified as examples of the first gas can be used. In step E performed after step D ends, the fourth gas supply system supplies the fourth gas to the wafer 200 in the processing chamber 201, that is, to the wafer 200 from which the first gas has been removed and on which the second gas is adsorbed on the surface. As the processing conditions when supplying the fourth gas in this step, the following can be exemplified: Processing temperature: 350 to 700 °C, preferably 500 to 600 °C; Processing pressure: 1 to 10000 Pa, preferably 10 to 1333 Pa; Fourth gas supply flow rate: 0.01 to 3 slm, preferably 0.1 to 1 slm; Fourth gas supply time: 10 to 120 seconds, preferably 20 to 60 seconds; Inert gas supply flow rate (for each gas supply pipe): 0 to 10 slm. By supplying the fourth gas to the wafer 200 under the above processing conditions, the fourth gas and / or the fourth element contained in the fourth gas can be adsorbed on the portion of the surface of the wafer 200 where the second gas is not adsorbed (see (c) in FIG. 6). More specifically, by supplying the fourth gas to the wafer 200 under the above processing conditions, the fourth gas etc. can be adsorbed on the surface of the wafer 200 to form the third layer 600 containing the second element and the fourth element (see (c) in FIG. 6). It should be noted that in (c) of FIG. 6, the fourth gas and / or the fourth element contained in the fourth gas is represented by the character δ. Hereinafter, the fourth gas and / or the fourth element contained in the fourth gas may sometimes be referred to as the fourth gas etc. In this modification example, the same effect or a part of the effect as in the above method can also be obtained. Further, in this modification example, by further removing the first gas on the surface of the wafer 200 in step D, a layer containing the second element and not containing the first element can be uniformly formed on the surface of the wafer 200 (see (b) in FIG. 6). Furthermore, by supplying the fourth gas in step E, the third layer 600 containing the second element and the fourth element can be uniformly formed on the surface of the wafer 200 (see (c) in FIG. 6). In addition, the controllability of the amount of the second element contained in the third layer 600 can be improved. (Modification example 3) It is also possible to perform the cycle of step A, step B, step E, and step C a predetermined number of times (p 1 times, p 1 is an integer of 1 or 2 or more). (First gas → purification → second gas → purification → fourth gas → purification → third gas → purification) × p 1In this modification example, the same effects as those in the above-described method or a part of the effects can also be obtained. Further, in this modification example, a layer including a first element, a second element, a third element, and a fourth element is formed. Thereby, a film including the second element and the fourth element can be uniformly formed on the surface of the wafer 200. In other words, the second element and the fourth element with a sufficiently controlled amount can be added to the film mainly composed of the first element and the third element. Further, as in the processing sequence shown below, the cycles of performing step A, step B, and step C may be repeated a predetermined number of times (p 1 times, p 1 is an integer of 1 or more), and further, for the cycle of performing the cycles of step A, step E, and step C in sequence a predetermined number of times (p 2 times, p 2 is an integer of 1 or more), and then the cycle of performing a predetermined number of times (p 2 times) may be repeated a predetermined number of times (p 3 times, p 3 is an integer of 1 or more). {(First gas → purification → second gas → purification → third gas → purification) × p 1 → (First gas → purification → fourth gas → purification → third gas → purification) × p 2} × p 3Here, in this modification example, as the fourth element, for example, one or more elements different from the first element and the second element among the elements exemplified as the first element are used. Further, as the fourth gas, for example, a gas containing one or more of the gases exemplified as the first gas can be used. In this modification example, the same effect or a part of the effect as that of the above-described method can also be obtained. Further, in this modification example, a layer containing the first element, the second element, and the third element, and a layer containing the first element, the fourth element, and the third element are respectively formed. Thereby, a film containing the second element and the fourth element can be uniformly formed on the surface of the wafer 200. In other words, the second element and the fourth element, the amounts of which have been sufficiently controlled, can be added to the film mainly composed of the first element and the third element. <Other aspects of the present invention> Above, the aspects of the present invention have been specifically described. However, the present invention is not limited to the above-described aspects, and various modifications can be made without departing from the gist thereof. For example, when the adsorption amount of the second gas on the surface of the wafer 200 is set to 0.001 to 30.0% of the total amount of the adsorption amount of the first gas and the adsorption amount of the second gas, the deviation of the adsorption amount of the second gas on the surface of the wafer 200 tends to increase. Further, when the adsorption amount of the second gas is set to 0.005 to 10.0% or less of the total amount of the adsorption amount of the first gas and the adsorption amount of the second gas, the deviation of the adsorption amount of the second gas on the surface of the wafer 200 tends to increase. Furthermore, when the adsorption amount of the second gas is set to 0.010 to 5.0% of the total amount of the adsorption amount of the first gas and the adsorption amount of the second gas, the deviation of the adsorption amount of the second gas on the surface of the wafer 200 becomes significant. In these cases, the controllability of the adsorption amount of the second gas on the surface of the wafer 200 can also be improved by the technology of the present invention. For example, in the above-described method, the amount of the second gas adsorbed on the surface of the wafer 200 in step B can also be controlled by the supply conditions of the first gas in step A. The supply conditions of the first gas refer to, for example, at least one of the supply flow rate of the first gas, the supply time of the first gas, the partial pressure of the first gas in the processing chamber 201 when the first gas is supplied, or the concentration of the first gas in the processing chamber 201 (the ratio of the first gas to the inert gas). In this method, the same effect as that of the above-described method can also be obtained. FIG. 7 is a graph showing the relationship between the supply time of the first gas in step A and the concentration of the second element in the film when a film containing the first element, the second element, and the third element is formed by the processing sequence described in the above-described method. The horizontal axis of the graph of FIG. 7 represents the supply time of the first gas per cycle. The vertical axis of the graph of FIG. 7 represents the concentration of the second element in the film, and the unit is [atomic% (at.%)]. As can be seen from FIG. 7, as the supply time of the first gas per cycle becomes longer and the amount of the first gas adsorbed on the first adsorption site increases, the concentration of the second element in the film decreases.Thus, when performing step A under conditions that make the adsorption amount of the first gas adsorbed on the surface of the wafer 200 unsaturated, the longer the supply time of the first gas in step A, the more the amount of the second gas adsorbed on the surface of the wafer 200 in step B can be reduced. Similarly, when increasing the supply flow rate of the first gas in step A, increasing the partial pressure of the first gas in the processing chamber 201 during the supply of the first gas, or increasing the concentration of the first gas in the processing chamber 201, the amount of the first gas adsorbed on the first adsorption site in step A increases. Therefore, in these cases, the amount of the second gas adsorbed on the surface of the wafer 200 in step B becomes less. In this way, by controlling the amount of the first gas adsorbed on the first adsorption site according to the supply conditions of the first gas in step A, the amount of the second gas adsorbed on the surface of the wafer 200 in step B can be controlled. In addition, for example, in the above method, the amount of the second gas adsorbed on the surface of the wafer 200 in step B can also be controlled through the supply conditions of the second gas in step B. The supply conditions of the second gas refer to at least one of, for example, the supply flow rate of the second gas, the supply time of the second gas, the partial pressure of the second gas in the processing chamber 201 during the supply of the second gas, or the concentration of the second gas in the processing chamber 201 (the ratio of the second gas to the inert gas). In this method, the same effect as the above method can also be obtained. FIG. 8 is a graph showing the relationship between the supply flow rate of the second gas in step B and the concentration of the second element in the film when forming a film containing the first element, the second element, and the third element by the processing sequence described in the above method. The horizontal axis of the graph in FIG. 8 represents the supply amount of the second gas per cycle. The vertical axis of the graph in FIG. 8 represents the concentration of the second element in the film, and the unit is [atomic% (at.%)]. It can be seen from FIG. 8 that the more the supply amount of the second gas per cycle and the more the amount of the first gas adsorbed on the first adsorption site increases, the higher the concentration of the second element in the film. That is, the more the supply amount of the second gas in step B increases, the more the amount of the second gas adsorbed on the surface of the wafer 200 in step B can be increased. Similarly, when increasing the supply flow rate of the second gas in step B, increasing the partial pressure of the second gas in the processing chamber 201 during the supply of the second gas, or increasing the concentration of the second gas in the processing chamber 201, the amount of the second gas adsorbed on the first adsorption site in step B increases. Therefore, in these cases, the amount of the second gas adsorbed on the surface of the wafer 200 in step B becomes more. In this way, by controlling the amount of the second gas adsorbed on the first adsorption site according to the supply conditions of the second gas in step B, the amount of the second gas adsorbed on the surface of the wafer 200 in step B can be controlled. For example, in the above method, the case where step B is performed under conditions where the adsorption amount of the second gas on the surface of the wafer 200 does not reach saturation is exemplified.However, the present invention is not limited to this manner. For example, step B can also be performed in the following manner: causing the second gas to adsorb onto all of the first adsorption sites that have not adsorbed the first gas. In this manner, the same effect as the above-described manner can also be obtained. In this manner, compared with the case of performing under conditions where saturation does not occur, the controllability of the adsorption amount of the second gas can be further improved. For example, in the above-described manner, the case where step A starts before step B was exemplified. However, the present invention is not limited to this manner. For example, step A can be partially performed simultaneously with step B, and step A can start simultaneously with step B. In this case, the same effect as the above-described manner can also be obtained. Generally, when there are hydrophilic ligands (hydrophilic adsorption sites are formed) on the surface of the wafer 200, a gas having a hydrophilic ligand (hydrophilic gas) becomes less likely to adsorb onto the surface of the wafer 200. Similarly, when there are hydrophobic ligands (hydrophobic adsorption sites are formed) on the surface of the wafer 200, a gas having a hydrophobic ligand (hydrophobic gas) becomes less likely to adsorb onto the surface of the wafer 200. Here, the hydrophilic ligand refers to a ligand having a charge or a high polarity, such as a halide (e.g., fluoride, chloride, bromide, iodide), an alkoxide group (e.g., -O(CH 3 ), -O(CH 2 CH 3 ))), an amino group (e.g., -NH 2 , -NH(CH 3 ), -N(CH 3 )) 2 , -NH(CH 2 CH 3 ), -N(CH 2 CH 3 )) 2 ), etc. In addition, the hydrophobic ligand refers to an alkyl group (e.g., -CH 3 , -CH 2 CH 3 ), a hydrogen group (-H), a cycloalkyl group (e.g., -C 3 H 5 , -C 4 H 7 , -C 5 H 9 , -C 6 H 11 ), a functional group having a carbocyclic structure (such as phenyl (-C 6 H 5)), cyclopentadienyl (Cp)), etc. Thus, for example, in step A, when the first gas adsorbed to the first adsorption site forms hydrophilic adsorption sites on the surface of the wafer 200, it is preferable that the second gas supplied in step B is a hydrophilic gas. In addition, in step A, when the first gas adsorbed to the first adsorption site forms hydrophobic adsorption sites on the surface of the wafer 200, it is preferable that the second gas supplied in step B is a hydrophobic gas. In either case, the first gas becomes more likely to inhibit the adsorption of the second gas, etc., to the wafer 200, so the second gas becomes less likely to adsorb to the first gas, etc., that has already been adsorbed to the surface of the wafer 200. Therefore, the second gas becomes more likely to preferentially adsorb to the first adsorption sites on the surface of the wafer 200 where the first gas, etc., is not adsorbed. Therefore, in step B, the adsorption amount of the second gas on the surface of the wafer 200 becomes less likely to exceed the desired amount. Here, as the hydrophilic gas, for example, a gas having a hydrophilic ligand among the gases exemplified as the first gas can be used. In addition, as the hydrophilic gas, even if it is not a gas exemplified as the first gas, a gas having a hydrophilic ligand can be appropriately used. Similarly, as the hydrophobic gas, for example, a gas having a hydrophobic ligand among the gases exemplified as the first gas can be used. As the hydrophobic gas, even if it is not a gas exemplified as the first gas, a gas having a hydrophobic ligand can be appropriately used. For example, in the above manner, the case where the second element contained in the second gas is different from the first element contained in the first gas is exemplified. However, the present invention is not limited to this manner. For example, the second element may be the same as the first element, and the second gas may be a gas having a different molecular structure from the first gas. In this case, the same effect as the above manner can also be obtained. In addition, in this case, a first layer 300 containing the first element can also be uniformly formed on the surface of the wafer 200. The recipes for each process are preferably prepared separately in advance according to the process content, and recorded and stored in the storage device 121c via a telecommunication line and an external storage device 123. And, at the start of each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe from among the multiple recipes recorded and stored in the storage device 121c according to the process content. Thereby, it is possible to reproducibly form films of various film types, composition ratios, film qualities, and film thicknesses with a single substrate processing apparatus. In addition, the burden on the operator can be reduced, and each process can be started quickly while avoiding operation errors. The above recipes are not limited to newly made ones. For example, they can also be prepared by changing the existing recipes already installed in the substrate processing apparatus. In the case of changing the recipe, the changed recipe can also be installed in the substrate processing apparatus via a telecommunication line and a recording medium on which the recipe is recorded.In addition, the input / output device 122 provided in the existing substrate processing apparatus can be operated to directly change the existing recipe installed in the substrate processing apparatus. In the above-described manner, an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at once has been described. The present invention is not limited to the above-described manner, and for example, it can also be appropriately applied to a case where a film is formed using a single-wafer type substrate processing apparatus that processes one or more substrates at once. In addition, in the above-described manner, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present invention is not limited to the above-described manner, and it can also be appropriately applied when a film is formed using a substrate processing apparatus having a cold-wall type processing furnace. When using these substrate processing apparatuses, each process can be performed in the same processing sequence and processing conditions as those in the above-described manner and modified example, and the same effects as those in the above-described manner and modified example can be obtained. The above-described manner and modified example can be used in appropriate combination. The processing sequence and processing conditions at this time can be set to be the same as those in the above-described manner and modified example, for example. 200: Wafer (substrate) [Fig. 1] is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a diagram showing a part of the processing furnace 202 in a longitudinal sectional view. [Fig. 2] is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a diagram showing a part of the processing furnace 202 in a sectional view taken along line A-A of Fig. 1. [Fig. 3] is a schematic configuration diagram of a controller 121 of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a diagram showing a control system of the controller 121 in a block diagram. (a) to (c) in [Fig. 4] are partial enlarged sectional views showing an example of substances formed in each step of a processing sequence in one embodiment of the present invention; (a) in Fig. 4 is a partial enlarged sectional view of the surface of the wafer 200 after the first gas is adsorbed on the surface of the wafer 200; (b) in Fig. 4 is a partial enlarged sectional view of the surface of the wafer 200 after the first gas and the second gas are adsorbed on the surface of the wafer 200 to form the first layer 300; (c) in Fig. 4 is a partial enlarged sectional view of the surface of the wafer 200 after the first layer 300 formed on the surface of the wafer 200 is modified into the second layer 400 through the third gas. [Fig. 5] is a partial enlarged sectional view of a film formed on the surface of the wafer 200 in Modification 1 of the present invention. (a) to (c) in [Fig. 6] are partial enlarged sectional views showing an example of substances formed in each step of a processing sequence in Modification 2 of the present invention; (a) in Fig. 6 is a partial enlarged sectional view of the surface of the wafer 200 after the first gas and the second gas are adsorbed on the surface of the wafer 200 to form the first layer 300; (b) in Fig. 6 is a partial enlarged sectional view of the surface of the wafer 200 after the first gas among the first gas and the second gas adsorbed on the surface of the wafer 200 is removed; (c) in Fig. 6 is a partial enlarged sectional view of the surface of the wafer 200 after the fourth gas is adsorbed on the surface of the wafer 200 from which the first gas has been removed and the third layer 600 is formed. [Fig. 7] is a diagram showing the relationship between the supply time of the first gas per cycle and the concentration of the second element in the film when forming a film using the processing sequence in one embodiment of the present invention. [Fig. 8] is a diagram showing the relationship between the supply amount of the second gas per cycle and the concentration of the second element in the film when forming a film using the processing sequence in one embodiment of the present invention. 200: Wafer (substrate) 300: First layer 400: Second layer α: First gas β: Second gas γ: Third gas

Claims

1. A substrate processing method comprising: (a) supplying a first gas to a substrate having a predetermined surface with first adsorption sites, wherein, The first gas is a gas that inhibits the adsorption of the second gas at the first adsorption site; and (b) the process of supplying the second gas to the substrate under the condition that the amount of the second gas adsorbed on the predetermined surface is self-limiting, (a) is started simultaneously with (b) or before (b), the first gas adsorbs a greater amount than the second gas on the predetermined surface, the first gas is a gas containing a first element and a halogen element, the second gas is a gas containing a second element different from the first element and a halogen element, and through (a) and (b), a first layer containing the first element and the second element is formed on the predetermined surface.

2. The substrate processing method as described in claim 1, wherein, By controlling the supply conditions of the first gas in (a), the amount of the second gas adsorbed on the predetermined surface in (b) is thereby controlled.

3. The substrate processing method as described in claim 2, wherein, (a) is carried out under the condition that the amount of the first gas adsorbed on the predetermined surface becomes self-limiting and the amount of the first gas adsorbed on the predetermined surface becomes unsaturated.

4. The substrate processing method as described in claim 1, wherein, By controlling the supply conditions of the second gas in (b), the amount of the second gas adsorbed on the predetermined surface in (b) is thereby controlled.

5. The substrate processing method as described in claim 1, wherein, (b) is carried out under the condition that the adsorption amount of the aforementioned second gas on the aforementioned predetermined surface is not saturated.

6. The substrate processing method as described in claim 1, wherein, In (b), the aforementioned second gas is adsorbed onto all of the aforementioned first adsorption sites that did not adsorb the aforementioned first gas.

7. The substrate processing method as described in claim 1, wherein, It also includes (c) forming the first adsorption site on at least a portion of the aforementioned predetermined surface, and includes performing (c) a predetermined number of times in a first cycle following (a) and (b).

8. The substrate processing method as described in claim 7, wherein, It also includes performing the second cycle of (a) and (c) a predetermined number of times, and performing the aforementioned first cycle and the aforementioned second cycle a predetermined number of times respectively.

9. The substrate processing method as described in claim 7, wherein, In (c), a third gas is supplied to the aforementioned substrate to form the aforementioned first adsorption sites on at least a portion of the aforementioned predetermined surface.

10. The substrate processing method as described in claim 9, wherein, The aforementioned third gas has a third element. In (c), a second layer containing the aforementioned third element and having the aforementioned first adsorption sites is formed on at least a portion of the aforementioned predetermined surface.

11. The substrate processing method as described in claim 1, wherein, It also includes: (d) a process for removing at least a portion of the first gas adsorbed on the aforementioned predetermined surface.

12. The substrate processing method as described in claim 11, wherein, It also includes: (e) supplying a fourth gas having a fourth element and being a gas different from the first gas, and forming a third layer having the second and fourth elements on the predetermined surface.

13. The substrate processing method as described in claim 1, wherein, In (b), the aforementioned second gas is supplied from the side of the aforementioned substrate.

14. A method for manufacturing a semiconductor device, comprising: (a) supplying a first gas to a substrate having a predetermined surface having first adsorption sites, wherein, The first gas is a gas that inhibits the adsorption of the second gas on the predetermined surface; and (b) is an process of supplying the second gas to the substrate under the condition that the amount of the second gas adsorbed on the predetermined surface is self-limiting, wherein (a) is started simultaneously with (b) or before (b), the first gas adsorbs a greater amount than the second gas on the predetermined surface, the first gas is a gas containing a first element and a halogen element, the second gas is a gas containing a second element different from the first element and a halogen element, and through (a) and (b), a first layer containing the first element and the second element is formed on the predetermined surface.

15. A substrate processing apparatus comprising: a first gas supply system for supplying a first gas to a substrate having a predetermined surface having first adsorption sites, wherein, The first gas is a gas that inhibits the adsorption of the second gas on the predetermined surface; a second gas supply system supplies the second gas to the substrate; and a control unit configured to control the first gas supply system and the second gas supply system in a manner capable of performing the following processes: (a) supplying the first gas to the substrate; and (b) supplying the second gas to the substrate under the condition that the amount of the second gas adsorbed on the predetermined surface is self-limiting, wherein (a) starts simultaneously with or before (b), such that the first gas adsorbs a greater amount than the second gas on the predetermined surface, the first gas is a gas containing a first element and a halogen element, the second gas is a gas containing a second element different from the first element and a halogen element, and a first layer containing the first element and the second element is formed on the predetermined surface through (a) and (b).

16. A program that, via a computer, causes a substrate processing apparatus to execute the following sequence: (a) a sequence of supplying a first gas to a substrate having a predetermined surface with first adsorption sites, wherein, The first gas is a gas that inhibits the adsorption of the second gas on the predetermined surface; and (b) the sequence of supplying the second gas to the substrate under the condition that the amount of the second gas adsorbed on the predetermined surface is self-limiting, wherein (a) starts simultaneously with (b) or before (b), such that the first gas adsorbs a greater amount than the second gas on the predetermined surface, the first gas is a gas containing a first element and a halogen element, the second gas is a gas containing a second element different from the first element and a halogen element, and the first layer containing the first element and the second element is formed on the predetermined surface in the sequence of (a) and (b).

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