Substrate processing methods, semiconductor device manufacturing methods, substrate processing apparatus and processes

Abstract

The present invention provides a method for improving the uniformity of a film formed on the surface of a substrate. It includes performing the following steps (a) to (d): a first cycle forming a layer comprising a first element and a second element; (a) supplying a first feed gas having the first element to a substrate having recesses on its surface; (b) supplying a first adsorption-blocking gas to the substrate; (c) supplying a second feed gas having the second element different from the first element to the substrate; and (d) supplying a reactant gas to the substrate. In (a) and (b), functional groups formed on the substrate prevent the adsorption of the second feed gas onto the substrate. In at least a portion of (c), the second feed gas is supplied to the substrate having adsorbed the first feed gas and the first adsorption-blocking gas.

Description

Substrate processing method, semiconductor device manufacturing method, substrate processing device and program The present invention relates to a substrate processing method, a semiconductor device manufacturing method, a substrate processing device and a program. As a step in substrate processing (a step in manufacturing semiconductor devices), a film is sometimes formed on the surface of a substrate using a substance that inhibits other substances from adsorbing onto the substrate (for example, see Patent Document 1). [Prior Art Document] [Patent Document] Patent Document 1: Japanese Patent Application Laid-Open No. 2022-110465 (Problems to be Solved by the Invention) The present invention provides a technique for improving the uniformity of a film formed on a substrate surface. (Technical Means for Solving the Problems) According to one aspect of the present invention, a technique is provided, which comprises performing the following steps (a) to (d) to form a first cycle of forming a layer containing a first element and a second element: (a) supplying a first raw material gas containing the first element to a substrate having a recessed portion on its surface; (b) supplying a first adsorption-inhibiting gas to the substrate; (c) supplying a second raw material gas containing the second element different from the first element to the substrate; and (d) supplying a reaction gas to the substrate; wherein the functional groups formed on the substrate in (a) and (b) inhibit adsorption of the second raw material gas onto the substrate, and in at least a portion of (c), the second raw material gas is supplied to the substrate on which the first raw material gas and the first adsorption-inhibiting gas are adsorbed. (Compared to the efficacy of the prior art) 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> Below, one aspect of the present invention will be described primarily with reference to Figures 1 to 4 and Figures 5(a) to 5(c). The figures used in the following description are schematic diagrams, and the dimensional relationships and proportions of the elements shown in the figures may not necessarily correspond to actual conditions. Furthermore, the dimensional relationships and proportions of the elements may not necessarily correspond across the multiple figures. (1) Configuration of Substrate Processing Apparatus As shown in Fig. 1 , a processing furnace 202 includes a heater 207 as a temperature adjustment unit (heating unit). The heater 207 also functions as an activation mechanism (excitation unit) for thermally activating (exciting) a gas. A reaction tube 203 is disposed inside the heater 207. A manifold 209 is disposed below the reaction tube 203, and 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 primarily constitute a processing vessel (reaction container). A processing chamber 201 is formed within the processing container. The processing chamber 201 is configured to accommodate wafers 200, serving as substrates. Wafers 200 are processed within the processing chamber 201. Nozzles 249a to 249c serving as first to third supply units are provided in the processing chamber 201. The nozzles 249a to 249c are also referred to as first to third nozzles, respectively. Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively. Gas supply pipes 232a through 232c are provided, in order from the upstream side of the gas flow, with mass flow controllers (MFCs) 241a through 241c, which function as flow controllers (flow control units), and valves 243a through 243c, which function as on-off valves. Gas supply pipes 232d and 232f are connected to gas supply pipe 232a downstream of valve 243a. Gas supply pipes 232e and 232g are connected to gas supply pipe 232b downstream of valve 243b. Gas supply pipe 232h is connected to gas supply pipe 232c downstream of valve 243c. MFCs 241d through 241h and valves 243d through 243h are provided in order from the upstream side of the gas flow. As shown in FIG2 , nozzles 249 a through 249 c are respectively disposed in the space between the inner wall of reaction tube 203 and wafer 200. Nozzles 249 a and 249 c are arranged on either side of a straight line L passing through nozzle 249 b and the center of exhaust port 231 a. Nozzles 249 a through 249 c are respectively provided with gas supply holes 250 a through 250 c for supplying gas toward wafer 200. Multiple gas supply holes 250 a through 250 c are provided from the bottom to the top of each nozzle 249 a through 249 c. A first precursor gas is supplied into the processing chamber 201 through the gas supply pipe 232 a , the MFC 241 a , the valve 243 a , and the nozzle 249 a . A second precursor gas is supplied into the processing chamber 201 through the gas supply pipe 232 b , the MFC 241 b , the valve 243 b , and the nozzle 249 b . A reaction gas (reactant) is supplied into the processing chamber 201 through the gas supply pipe 232 c , the MFC 241 c , the valve 243 c , and the nozzle 249 c . A first adsorption inhibitor gas (first inhibitor) is supplied into the processing chamber 201 via the gas supply pipe 232d, the MFC 241d, the valve 243d, the gas supply pipe 232a, and the nozzle 249a. The first adsorption inhibitor gas is a gas that inhibits the second source gas from being adsorbed on the wafer 200. A second adsorption inhibitor gas is supplied into the processing chamber 201 via the gas supply pipe 232e, the MFC 241e, the valve 243e, the gas supply pipe 232b, and the nozzle 249b. The second adsorption inhibitor gas is a gas that inhibits the first source gas from being adsorbed on the wafer 200. Inert gas is supplied into the processing chamber 201 through the gas supply pipes 232f to 232h, MFCs 241f to 241h, valves 243f to 243h, gas supply pipes 232a to 232c, and nozzles 249a to 249c. The inert gas functions as a purge gas, carrier gas, dilution gas, and the like. The first raw material gas supply system is primarily composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. The second raw material gas supply system is primarily composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. The reaction gas supply system is primarily composed of the gas supply pipe 232c, the MFC 241c, and the valve 243c. The first adsorption-inhibiting gas supply system is primarily composed of the gas supply pipe 232d, the MFC 241d, and the valve 243d. The second adsorption-inhibiting gas supply system is primarily composed of the gas supply pipe 232e, the MFC 241e, and the valve 243e. The inert gas supply system is primarily composed of the gas supply pipes 232f-232h, the MFCs 241f-241h, and the valves 243f-243h. The nozzles connected to the gas supply pipes constituting each of the above-mentioned supply systems may also be included in each of these supply systems. Any or all of the various supply systems described above may be configured as a centralized supply system 248 that integrates valves 243a to 243h, MFCs 241a to 241h, and the like. The centralized supply system 248 is connected to the gas supply pipes 232a to 232h, respectively, and is configured so that the supply of various substances (gases) into the gas supply pipes 232a to 232h, i.e., the opening and closing of the valves 243a to 243h, or the flow rate adjustment by the MFCs 241a to 241h, is controlled by a controller 121 (described later). An exhaust pipe 231 is connected to the lower side wall of the reaction tube 203 and is provided with an exhaust port 231a for exhausting the atmosphere within the processing chamber 201. A vacuum pump 246, serving as a vacuum exhaust device, is connected to the exhaust pipe 231 via a pressure sensor 245, a pressure detector (pressure detection unit) that detects the pressure within the processing chamber 201, and an APC (Auto Pressure Controller) valve 244, a pressure regulator (pressure adjustment unit). The APC valve 244 operates while the vacuum pump 246 is in operation, enabling vacuum evacuation and stopping of the processing chamber 201. The APC valve 244 is further configured to adjust the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is in operation, thereby regulating the pressure within the processing chamber 201. The exhaust system primarily comprises the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. It is also conceivable that the vacuum pump 246 could also be included in the exhaust system. A sealing cap 219 is provided below the manifold 209 to airtightly seal the lower end opening of the manifold 209. An O-ring 220b, serving as a sealing member and in contact with the lower end of the manifold 209, is provided on the upper surface of the sealing cap 219. A rotating mechanism 267 is provided below the sealing cap 219. A rotating shaft 255 of the rotating mechanism 267 passes through the sealing cap 219 and is connected to the wafer boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217. The sealing cap 219 is configured to be vertically raised and lowered by a wafer boat elevator 115 serving as an elevating mechanism provided outside the reaction tube 203. The wafer boat elevator 115 is configured as a transport device (transport mechanism) that transports the wafer 200 into and out of the processing chamber 201 by raising and lowering the sealing cap 219. A shutter 219s is provided below the manifold 209 to airtightly seal the lower opening of the manifold 209 when the seal cap 219 is lowered and the wafer boat 217 is unloaded from the processing chamber 201. An O-ring 220c, serving as a sealing member, is provided on the upper surface of the shutter 219s and abuts against the lower end of the manifold 209. The opening and closing movements (such as lifting and rotating movements) of the shutter 219s are controlled by a shutter opening and closing mechanism 115s. The wafer boat 217, serving as a substrate support, is configured to support, for example, 25 to 200 wafers 200 in a horizontal position in multiple stages. In this specification, numerical ranges such as "25 to 200 wafers" are intended to include both the lower and upper limits of the range. Thus, for example, "25 to 200 wafers" means "25 or more and 200 or less wafers." The same applies to other numerical ranges. Heat shields 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages at the bottom of the wafer boat 217. A temperature sensor 263 is installed within the reaction tube 203 as a temperature detector. The power supplied to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, thereby achieving a desired temperature distribution within the processing chamber 201 or on the wafers 200. The temperature sensor 263 is installed along the inner wall of the reaction tube 203. As shown in FIG3 , the controller 121, which is a control unit (control means), is configured as a computer including a central processing unit (CPU) 121a, a random access memory (RAM) 121b, a memory device 121c, and an I / O (Input / Output) port 121d. The RAM 121b, the memory device 121c, and the I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. The controller 121 is connected to an input / output device 122, such as a touch panel. Furthermore, the controller 121 can be connected to an external memory device 123. Furthermore, the substrate processing apparatus can be configured to include a single control unit or multiple control units. That is, the control for performing the processing sequence described below can be performed using a single control unit, or multiple control units can be used. Furthermore, the multiple control units can be configured as a control system interconnected via a wired or wireless communication network, or the control for performing the processing sequence described below can be performed by the entire control system. In this specification, when the term "control unit" is used, it may include not only one control unit but also a plurality of control units and a control system composed of a plurality of control units. The memory device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. In the memory device 121c, a control program for controlling the action of the substrate processing device, a process recipe that records the program or conditions for the substrate processing described later, etc., are recorded and stored in a readable manner. The process recipe is composed in a manner that enables the substrate processing device to execute each program in the substrate processing described later and obtain a predetermined result using the controller 121, and functions as a program. Hereinafter, process recipes, control programs, etc. are collectively referred to as programs. In addition, process recipes are also referred to as recipes. When the word "program" is used in this specification, sometimes only the recipe is included alone, sometimes only the control program is included alone, or sometimes both of them are included. RAM 121b is configured as a memory area (working area) that temporarily holds the program, data, etc. read by the CPU 121a. The I / O port 121d is connected to the MFCs 241a to 241h, valves 243a to 243h, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, shutter opening and closing mechanism 115s, and the like. The CPU 121a is configured to read and execute a control program from the memory device 121c, and to read a recipe from the memory device 121c based on input of an operation command from the input / output device 122. In accordance with the contents of the read recipe, the CPU 121a is configured to control the flow rate adjustment of various substances (gases) by the MFCs 241a to 241h, the opening and closing of the valves 243a to 243h, the opening and closing of the APC valve 244 and the pressure adjustment by the APC valve 244 using the pressure sensor 245, the starting and stopping of the vacuum pump 246, the temperature adjustment of the heater 207 using the temperature sensor 263, the rotation and rotation speed adjustment of the wafer boat 217 by the rotation mechanism 267, the raising and lowering of the wafer boat 217 by the wafer elevator 115, and the opening and closing of the shutter 219s by the shutter opening and closing mechanism 115s. The controller 121 can be constructed by installing the above-mentioned program recorded and stored in the external memory device 123 on a computer. The external memory device 123 includes, for example, magnetic disks such as HDD, optical disks such as CD, optical magnetic disks such as MO, semiconductor memories such as USB memory, SSD, etc. The memory device 121c and the external memory device 123 constitute a recording medium that can be read by a computer. Hereinafter, these will be collectively referred to as recording media. In this specification, when the term recording medium is used, sometimes only the memory device 121c is included alone, sometimes only the external memory device 123 is included alone, or sometimes both of them are included. In addition, instead of using the external memory device 123, it is also possible to use a communication means such as the Internet and a dedicated line to provide the program to the computer. (2) Substrate Processing Step Using the aforementioned substrate processing apparatus, as one step in the semiconductor device manufacturing process, a method for processing a substrate, specifically, an example of a processing sequence for forming a film on a wafer 200 having recessed portions such as trenches, grooves, or holes formed on its surface, which are three-dimensional structures, will be described primarily with reference to FIG. 4 and FIG. 5(a) to FIG. 5(c). In the following description, the operations of the various components of the substrate processing apparatus are controlled by a controller 121. In the processing sequence of this embodiment, there is a first cycle of performing the following (a) to (d) to form a layer containing a first element and a second element, (a) a step of supplying a first raw material gas having the first element to a wafer 200 having a recessed portion on its surface, (b) a step of supplying a first adsorption inhibiting gas to the wafer 200, (c) a step of supplying a second raw material gas having a second element different from the first element to the wafer 200, (d) a step of supplying a reaction gas to the wafer 200; and, in (a) and (b), the functional group formed on the wafer 200 hinders the adsorption of the second raw material gas onto the wafer 200, and in at least a part of (c), the second raw material gas is supplied to the wafer 200 on which the first raw material gas and the first adsorption inhibiting gas are adsorbed. As shown in FIG. 4 , in this embodiment, a case where a cycle of (a), (b), (c), and (d) is performed in sequence a predetermined number of times (n times, where n is an integer greater than or equal to 1 or 2) is described. As shown in FIG. 4 , in this aspect, a case where the second source gas is supplied to the wafer 200 on which the first source gas and the first adsorption inhibiting gas are adsorbed in all of (c) will be described. In this specification, for convenience, the above-mentioned processing sequence may be expressed as follows. The same expression is also used in the following description of modifications, other aspects, etc. (first source gas→first adsorption inhibitory gas→second source gas→reactive gas)×n In this specification, “→” in “first source gas→first adsorption inhibitory gas” indicates that a purge process is performed to purge the inside of the processing chamber 201 . The term "wafer" used in this specification sometimes means the wafer itself, and sometimes means a laminate of a wafer and a predetermined layer or film formed on its surface. The term "wafer surface technique" used in this specification sometimes means the surface of the wafer itself, and sometimes means the surface of a predetermined layer, etc. formed on the wafer. When it is stated in this specification that "a predetermined layer is formed on the wafer", it sometimes means that a predetermined layer is formed directly on the surface of the wafer itself, and sometimes means that a predetermined layer is formed on a layer, etc. formed on the wafer. In this specification, the use of the term "substrate" is synonymous with the use of the term "wafer". The term "layer" used in this specification includes at least one of a continuous layer and a discontinuous layer. For example, a buildup layer may include a continuous layer, a discontinuous layer, or both. In this specification, when describing the situations in which the first raw gas, the first adsorption inhibitory gas, the second raw gas, the second adsorption inhibitory gas and the reaction gas are adsorbed on the surface of the wafer 200 or react, it not only includes the situations in which they are adsorbed and reacted on the surface of the wafer 200 in an undecomposed state, but also includes the situations in which the intermediates generated by their decomposition and detachment of their ligands are adsorbed and reacted relative to the surface of the wafer 200. (Wafer Filling and Boat Loading) Multiple wafers 200 are loaded (wafer filling) into the wafer boat 217. The shutter 219s is moved by the shutter opening and closing mechanism 115s, opening the lower end of the manifold 209 (shutter opening). The wafer boat 217, supporting multiple wafers 200, is then lifted by the boat elevator 115 and loaded into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b. Thus, as shown in FIG1 , the wafers 200 are prepared (delivered) into the processing chamber 201. (Pressure Adjustment and Temperature Adjustment) After the wafer boat is loaded, vacuum exhaust (decompression exhaust) is performed using the vacuum pump 246 to reduce the pressure (vacuum degree) in the processing chamber 201, i.e., the space where the wafers 200 are located. At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. In addition, the heater 207 is used to heat the wafers 200 in the processing chamber 201 to the required processing temperature. At this time, the power supplied to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 to achieve the required temperature distribution in the processing chamber 201. In addition, the rotation mechanism 267 starts to rotate the wafers 200. The exhaust in the processing chamber 201 and the heating and rotation of the wafers 200 are all continued for at least until the processing of the wafers 200 is completed. (Film Formation Process) Thereafter, the following steps A, B, C, and D are performed in sequence. [Step A] In this step, a first source gas containing a first element is supplied to the wafer 200 in the processing chamber 201 , that is, the wafer 200 having a recessed portion on its surface. Specifically, valve 243a is opened to allow the first source gas to flow into gas supply pipe 232a. The first source gas is flow-regulated by MFC 241a, supplied into processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, the first source gas is supplied to wafer 200 from the side of wafer 200 (first source gas supply). Alternatively, valves 243f through 243h may be opened to supply inert gas into processing chamber 201 via nozzles 249a through 249c, respectively. As the processing conditions when supplying the first raw material gas in this step, the following are exemplified: processing temperature: 350~700℃, preferably 500~600℃, processing pressure: 1~10000Pa, preferably 10~1333Pa, first raw material gas supply flow rate: 0.01~3slm, preferably 0.1~1slm, first raw material gas supply time: 10~120 seconds, preferably 20~60 seconds, inert gas supply flow rate (each gas supply pipe): 0~10slm. In this specification, the processing temperature refers to the temperature of wafer 200 or the temperature within processing chamber 201, and the processing pressure refers to the pressure within processing chamber 201. Furthermore, the processing time refers to the duration of the processing. Furthermore, the supply flow rate refers to the flow rate of gas supplied to processing chamber 201. Furthermore, when the supply flow rate includes 0 slm, 0 slm indicates that the substance (gas) is not supplied to processing chamber 201. This also applies to the following description. By supplying the first raw material gas to the wafer 200 under the above-mentioned processing conditions, the first raw material gas can be adsorbed on the adsorption sites present on the surface of the wafer 200 (refer to Figure 5(a)). Specifically, thereby, the first raw material gas can be discontinuously adsorbed on at least a portion of the upper surface and inner surface (the side wall surface and bottom surface inside the recess) of the recess (refer to Figure 5(a)). More specifically, thereby, the first raw material gas can be discontinuously adsorbed on the entire surface from the opening side to the deep side of the recess. In addition, the predetermined functional groups possessed by the first raw material gas are exposed on the upper surface and inner surface of the recess where the first raw material gas is adsorbed. Hereinafter, the "opening side of the recess" will be referred to as the "opening side", and the "deep side of the recess" will be referred to as the "deep side". In addition, in this specification, the "deep side of the recess" refers to a portion, such as the bottom of the recess, which is difficult for the gas supplied to the wafer 200 to reach compared to the opening side, and its surrounding area. As the first raw material gas, for example, a silane-based gas containing silicon (Si) as the first element can be used. As the silane-based gas, for example, a gas containing Si and a halogen, i.e., a halosilane-based gas, can be used. Halogens include chlorine (Cl), fluorine (F), bromine (Br), iodine (I), and the like. In other words, the halosilane-based gas has at least one halogen group, such as a chlorine (Cl) group, a fluorine (F) group, a bromine (Br) group, or an iodine (I) group, as a functional group. As the first raw material gas, for example, monochlorosilane (SiH 3Cl) gas, dichlorosilane (SiH 2Cl 2) Gas, trichlorosilane (SiHCl 3) Gas, tetrachlorosilane (SiCl 4) Gas, hexachlorodisilane (Si 2Cl 6) Gas, octachlorotrisilane (Si 3Cl 8) Chlorosilane-based gases such as chlorosilane gas. As the first raw material gas, one or more of these can be used. As the first raw material gas, in addition to the chlorosilane-based gas, for example, tetrafluorosilane (SiF 4) Gas, trifluorosilane (SiHF 3) Gas, difluorosilane (SiH 2F 2) Gases such as fluorosilane gas or tetrabromosilane (SiBr 4) Gas, tribromosilane (SiHBr 3) Gas, dibromosilane (SiH 2Br 2) Gases such as bromosilane gas or tetraiodosilane (SiI 4) Gas, triiodosilane (SiHI 3) Gas, diiodosilane (SiH 2I 2) Iodosilane-based gases such as iodosilane gas. As the first raw material gas, one or more of these can be used. In addition, as the first raw material gas, for example, a gas containing Si as the first element and an organic ligand can be used. As the gas containing Si and an organic ligand, for example, tetrakis(dimethylamino)silane (Si[N(CH 3) 2] 4) Gas, dimethylaminosilane (Si[N(CH 3) 2] 3H) gas, bis(diethylamino)silane (Si[N(C 2H 5) 2] 2H 2) Gas, bis(tertiary butylamino)silane (SiH 2[NH(C 4H 9)] 2) Gas, (diisopropylamino)silane (SiH 3[N(C 3H 7) 2]) gas or other aminosilane gas. In addition, as the first raw material gas, a gas having Si as the first element and a hydrogen (H) group can be used. As the gas having Si and H groups, for example, monosilane (SiH 4) Disilane (Si 2H 6) As the first raw material gas, one or more of these can be used. As the first raw material gas, in addition to these, a gas containing Si and an alkyl group as an organic ligand, i.e., an alkylsilane-based gas, can also be used. The alkyl group may be linear or branched. Examples of the alkyl group include methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, secondary butyl, and tertiary butyl. In addition, 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), boron (B), gallium (Ga), indium (In), phosphorus (P), carbon (C), etc. can be used. As the first raw material gas, for example, a gas containing the first element and a halogen element 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 dioxide dichloride (MoO 2Cl 2) Molybdenum oxide tetrachloride (MoOCl 4) Tantalum pentachloride (TaCl 5) Tantalum pentafluoride (TaF 5) Cobalt difluoride (CoF 2) Cobalt dichloride (CoCl 2) Yttrium trifluoride (YF 3) Yttrium chloride (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 chloride (AlCl 3) Aluminum trifluoride (AlF 3) etc. In addition, as the first raw material gas, for example, 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 3F), chloroform (CHCl 3) Methyl chloride (CH 3Cl), etc. As the first raw material gas, for example, a gas containing the first element and a Br group, or a gas containing the first element and an I group may be used. In addition, as the first raw material gas, for example, a gas containing the first element and an organic ligand, or a gas containing the first element and a hydrogen group can be used. As the organic ligand, for example, an alkyl group, a cycloalkyl group, an alkoxide group, a phenyl group, or a cyclopentadienyl group can be used. As the first raw material gas, for example, hexa(dimethylamino)ditungsten (W 2[N(CH 3) 2] 6) Bis(tertiary butylimide)bis(dimethylamide)tungsten (tC 4H 9NH) 2W=(Nt-C 4H 9) 2) Tetrakis(ethylmethylamino)titanium(Ti[N(C 2H 5)(CH 3)] 4) Bis(ethylcyclopentadienyl)ruthenium (Ru(CH 2CH 3) Cp) 2) Biscyclopentadienylruthenium (Ru(Cp) 2) Tetrakis(ethylmethylamino)hafnium (Hf[N(CH 3)(CH 2CH 3)] 4) Tetrakis(diethylamino)hafnium (Hf[N(CH 2CH 3) 2] 4) Tetrakis(dimethylamino)hafnium (Hf[N(CH 3) 2] 4) cyclopentadienyl hafnium ((Cp)Hf[N(CH 3) 2] 3) Tetrakis(ethylmethylamino)zirconium (Zr[N(CH 3) Cp] 4) Tetrakis(diethylamino)zirconium (Zr[N(CH 2CH 3) 2] 4) Tetrakis(dimethylamino)zirconium (Zr[N(CH 3) 2] 4) cyclopentadienyl zirconium ((Cp)Zr[N(CH 3) 2] 3) Trimethylaluminum (Al(CH 3) 3) Borane (BH 3) Trimethylgallium (Ga(CH 3) 3) Trimethylindium (In(CH 3) 3) Phosphine (PH 3) Methane (CH 4) etc. As the inert gas, nitrogen (N 2) Inert gases such as argon (Ar), helium (He), neon (Ne), and xenon (Xe). One or more of these inert gases may be used. This also applies to the steps described below. After the first source gas is adsorbed onto the surface of wafer 200 (the upper surface and inner surface of the recess), valve 243a is closed to stop the supply of the first source gas into processing chamber 201. Then, the processing chamber 201 is evacuated to remove gaseous substances remaining in the processing chamber 201. At this time, valves 243f to 243h are opened to supply an inert gas into the processing chamber 201 via nozzles 249a to 249c. The inert gas supplied from nozzles 249a to 249c acts as a purge gas, thereby purging (flushing) the space where wafer 200 is located, i.e., the interior of processing chamber 201. [Step B] After step A is completed, the first adsorption inhibiting gas is supplied to the wafer 200 in the processing chamber 201 , that is, to the wafer 200 after the first source gas is adsorbed on the inner surface of the recess. Specifically, valve 243d is opened to allow the first adsorption-inhibiting gas to flow into gas supply pipe 232d. The first adsorption-inhibiting gas is flow-controlled by MFC 241d and supplied into processing chamber 201 via nozzle 249a and exhausted from exhaust port 231a. At this point, the first adsorption-inhibiting gas is supplied to wafer 200 (first adsorption-inhibiting gas supply). Alternatively, valves 243f through 243h may be opened to supply inert gas into processing chamber 201 via nozzles 249a through 249c, respectively. The following are examples of process conditions for supplying the first adsorption-inhibiting gas in this step: Process temperature: 400-900°C, preferably 500-800°C; Process pressure: 1-2666 Pa, preferably 10-1333 Pa; First adsorption-inhibiting gas supply flow rate: 0.001-2 slm, preferably 0.01-1 slm; First adsorption-inhibiting gas supply time: 1-40 seconds, preferably 2-20 seconds; Inert gas supply flow rate (per gas supply pipe): 0-10 slm. Other process conditions can be the same as those for supplying the first raw material gas in step A. The supply time of the first adsorption-inhibiting gas is preferably shorter than the supply time of the first raw material gas in step A. Furthermore, the process pressure (total pressure) in this step is preferably lower than the process pressure in step A. Furthermore, the supply flow rate of the first adsorption-inhibiting gas is preferably lower than the supply flow rate of the first raw material gas in step A. Furthermore, the supply flow rate of the inert gas in this step is preferably higher than the supply flow rate of the inert gas in step A. Furthermore, the partial pressure of the first adsorption inhibiting gas is preferably lower than the partial pressure of the first source gas in step A. The molar fraction of the first adsorption inhibiting gas is preferably smaller than the molar fraction of the first source gas in step A. By supplying the first adsorption-inhibiting gas to the wafer 200 under the aforementioned processing conditions, the first adsorption-inhibiting gas can be adsorbed onto adsorption sites present on the surface of the wafer 200 (see FIG5(b)). Specifically, this allows the first adsorption-inhibiting gas to be discontinuously adsorbed onto at least a portion of the upper and inner surfaces of the recess (see FIG5(b)). More specifically, this allows the first adsorption-inhibiting gas to be preferentially adsorbed onto locations closer to the opening than to the deep side (see FIG5(b)). Furthermore, on the upper and inner surfaces of the recess where the first adsorption-inhibiting gas is adsorbed, the predetermined functional groups of the first adsorption-inhibiting gas are exposed. By performing steps A and B under the above-described processing conditions, the exposure level of the first adsorption-inhibiting gas can be reduced to a level lower than that of the first source gas. In this specification, "gas exposure level" refers to the time-integrated value of the partial pressure of the gas. When the partial pressure of the gas is assumed to be constant, it can be calculated as the product of the partial pressure of the gas and the gas supply time. By performing steps A and B under the above-mentioned processing conditions, the amount of the first adsorption inhibitory gas adsorbed on the deep side can be made smaller than the amount of the first source gas adsorbed on the deep side (see FIG. 5( b )). As the first adsorption-inhibiting gas, a halogen-containing gas containing at least one of Cl, F, Br, and I can be used. The halogen-containing gas has at least one of a Cl group, a F group, a Br group, an I group, and other halogen groups as a functional group. As the first adsorption-inhibiting gas, for example, fluorine (F 2) Gas, chlorine (Cl 2) Gas, bromine (Br 2) Gas, iodine (I 2) Halogen element monomer gas such as gas, chlorine fluoride (ClF 3) Gas, bromine chloride (BrCl) gas, iodine chloride (ICl) gas, iodine fluoride (IF 5) Gas, bromine fluoride (BrF 3) gas, halogen compound gas such as iodine bromide (IBr) gas, hydrogen chloride (HCl) gas, hydrogen fluoride (HF) gas, hydrogen bromide (HBr) gas, hydrogen iodide (HI) gas, or a combination of these gases. In addition, as the first adsorption-inhibiting gas, a gas containing an organic compound can be used. As the gas containing an organic compound, a gas containing at least one selected from the group consisting of ether compounds, ketone compounds, amine compounds, organic hydrazine compounds, and compounds having a cyclic structure in their molecular structure can be used. As the gas containing an ether compound, a gas containing at least one of dimethyl ether, diethyl ether, methyl ethyl ether, propyl ether, isopropyl ether, furan, tetrahydrofuran, pyran, tetrahydropyran, etc. can be used. As the gas containing a ketone compound, a gas containing at least one of dimethyl ketone, diethyl ketone, methyl ethyl ketone, methyl propyl ketone, etc. can be used. As the gas containing an amine compound, a gas containing at least one of methylamine compounds such as monomethylamine, dimethylamine, and trimethylamine, ethylamine compounds such as monoethylamine, diethylamine, and triethylamine, and methylethylamine compounds such as dimethylethylamine and methyldiethylamine can be used. As the gas containing an organic hydrazine compound, a gas containing at least one of methylhydrazine-based gases such as monomethylhydrazine, dimethylhydrazine, and trimethylhydrazine can be used. As the gas containing a compound having a cyclic structure, a gas having a cyclic structure containing at least one of a cycloalkyl group, a benzene ring structure, and carbon in its molecular structure, such as methoxycyclopentane, anisole, and trimethylene oxide, can be used. As the first adsorption-inhibiting gas, one or more of these can be used. An alkyl-containing gas containing an alkyl group can also be used. As the first adsorption-inhibiting gas, methane (CH 4) Gas, ethane (C 2H 6) Gas, propane (C 3H 8) Gas, etc. As the first adsorption-inhibiting gas, it is preferable to use a gas that does not contain the first element. The molecular radius of the first adsorption-inhibiting gas used in this step is preferably smaller than the molecular radius of the first raw material gas used in step A. After the first barrier gas is adsorbed onto the surface of wafer 200 (the upper surface and inner surface of the recess), valve 243d is closed to stop the supply of the first barrier gas into processing chamber 201. Then, processing chamber 201 is evacuated to remove gaseous substances remaining in processing chamber 201. At this point, valves 243f to 243h are opened to supply an inert gas into processing chamber 201 via nozzles 249a to 249c. The inert gas supplied from nozzles 249a to 249c acts as a purge gas, thereby purging (flushing) the space in which wafer 200 is located, i.e., the interior of processing chamber 201. [Step C] After step B, a second source gas containing a second element different from the first element is supplied to wafer 200 in processing chamber 201 , that is, wafer 200 after the first source gas and the first adsorption inhibitory gas are adsorbed on the upper and inner surfaces of the recess. Specifically, valve 243b is opened to allow the second source gas to flow into gas supply pipe 232b. The second source gas is flow-regulated by MFC 241b, supplied into processing chamber 201 through nozzle 249b, and exhausted from exhaust port 231a. At this point, the second source gas is supplied to wafer 200 (second source gas supply). Alternatively, valves 243f-243h may be opened to supply inert gas into processing chamber 201 through nozzles 249a-249c, respectively. The following are examples of process conditions for supplying the second source gas in this step: Process temperature: 400-900°C, preferably 500-800°C; Process pressure: 1-5000 Pa, preferably 10-1333 Pa; Second source gas supply flow rate: 0.01-2 slm, preferably 0.1-1 slm; Second source gas supply time: 5-50 seconds, preferably 6-30 seconds; Inert gas supply flow rate (per gas supply pipe): 0-10 slm. Other process conditions can be the same as those for supplying the first source gas in step A. Here, it is preferred that the supply time of the second source gas be longer than the supply time of the first adsorption-inhibiting gas in step B. It is preferred that the process pressure in this step be higher than the process pressure in step B. It is preferred that the supply flow rate of the second source gas be greater than the supply flow rate of the first adsorption-inhibiting gas in step B. It is also preferred that the supply flow rate of the inert gas in this step be less than the supply flow rate of the inert gas in step B. Furthermore, the partial pressure of the second source gas is preferably higher than the partial pressure of the first adsorption inhibiting gas in step B. The molar fraction of the second source gas is preferably greater than the molar fraction of the first adsorption inhibiting gas in step B. By performing step B and step C under the above-mentioned processing conditions, the exposure amount of the second source gas can be made greater than the exposure amount of the first adsorption inhibiting gas. By supplying the second source gas to the wafer 200 under the above-mentioned processing conditions, the second source gas can be adsorbed on the surface of the wafer 200 where the first source gas and the first adsorption inhibiting gas are not adsorbed, that is, the adsorption sites remaining on the surface of the wafer 200 (see FIG. 5( c )). Here, the first raw material gas and the first adsorption-inhibiting gas system prevent the second raw material gas from being adsorbed onto the wafer 200. Specifically, the functional groups contained in the first raw material gas and the first adsorption-inhibiting gas and formed (exposed) on the upper surface and inner surface of the recess prevent the second raw material gas from being adsorbed onto the wafer 200 (the upper surface and inner surface of the recess). As a result, as shown in FIG5(c), the second raw material gas is not adsorbed on the first raw material gas and the first adsorption-inhibiting gas on the surface of the wafer 200. Therefore, by adjusting the processing conditions of step A and step B, controlling the amount of the first raw material gas and the first adsorption-inhibiting gas adsorbed on the wafer 200, etc., it is possible to control the amount of the second raw material gas adsorbed on the wafer 200. Here, in this specification, "the second raw material gas is not adsorbed on the first raw material gas and the first adsorption barrier gas" means, in addition to the situation that the second raw material gas is not adsorbed on the first raw material gas and the first adsorption barrier gas at all, it also includes the situation that very little second raw material gas is adsorbed on the first raw material gas and / or the first adsorption barrier gas. For example, it also includes the situation that the second raw material gas is adsorbed on about 1% of the first raw material gas and / or the first adsorption barrier gas on the wafer 200. Preferably, it includes the situation that the second raw material gas is adsorbed on less than 1% of the first raw material gas and / or the first adsorption barrier gas. By performing steps A-C, the first source gas, the first adsorption-inhibiting gas, and the second source gas are adsorbed onto adsorption sites provided on the surface of wafer 200, thereby forming a layer containing the first element and the second element (hereinafter sometimes referred to as the first layer). In other words, a first layer doped with the second element can be formed. By performing step B and step C under the above-mentioned processing conditions, the amount of the second source gas adsorbed on the deep side can be increased compared to the amount of the first adsorption inhibitory gas adsorbed on the deep side. Here, as the second element, an element not included in the first source gas as the first element among the elements listed as the first element, that is, an element different from the first element, can be used. Furthermore, as the second source gas, for example, a gas including the second element among the gases listed as the first source gas, such as a gas including the second element and a halogen element, a gas including the second element and an organic ligand, or a gas including the second element and an H group, can be used. When hydrophilic functional groups are formed on wafer 200 in steps A and B, it is preferred to use a gas containing hydrophilic functional groups in its molecular structure (hydrophilic gas) as the second source gas in step C. Here, a hydrophilic functional group refers to a functional group that easily generates partial charges due to a deviation in the electron distribution in the molecular structure. Alternatively, when hydrophobic functional groups are formed on wafer 200 in steps A and B, it is preferred to use a gas containing hydrophobic functional groups in its molecular structure (hydrophobic gas) as the second source gas in step C. Here, a hydrophobic functional group refers to a functional group that does not easily generate partial charges. After the second source gas is adsorbed onto the surface of wafer 200 (the inner surface of the recess), valve 243b is closed to stop the supply of the second source gas into processing chamber 201. Then, processing chamber 201 is evacuated to remove gaseous substances remaining in processing chamber 201. At this point, valves 243f to 243h are opened to supply an inert gas into processing chamber 201 via nozzles 249a to 249c. The inert gas supplied from nozzles 249a to 249c acts as a purge gas, thereby purging (flushing) the space where wafer 200 is located, i.e., the interior of processing chamber 201. [Step D] After step C, the reaction gas is supplied to the wafer 200 in the processing chamber 201 , that is, the wafer 200 after the first source gas, the first adsorption inhibitory gas, and the second source gas are adsorbed on the upper surface and inner surface of the recess. Specifically, valve 243c is opened to allow the reaction gas to flow into gas supply pipe 232c. The reaction gas is flow-regulated by MFC 241c, supplied into processing chamber 201 via nozzle 249c, and exhausted from exhaust port 231a. At this point, the reaction gas is supplied to wafer 200 (reaction gas supply). Alternatively, valves 243f through 243h may be opened to supply inert gas into processing chamber 201 via nozzles 249a through 249c, respectively. The following are examples of process conditions for supplying the reaction gas in this step: Process pressure: 1-4000 Pa, preferably 10-1000 Pa; Reaction gas supply flow rate: 0.1-10 slm, preferably 1-5 slm; Reaction gas supply time: 1-120 seconds, preferably 10-60 seconds. Other process conditions can be the same as those for supplying the first source gas in step A. By supplying the reactive gas to wafer 200 under the aforementioned processing conditions, at least a portion of the first layer formed on the inner surface of the recess reacts with the reactive gas and is modified. As a result, a modified layer of the first layer (hereinafter sometimes referred to as the second layer) is formed on the inner surface of the recess. When forming the second layer, the reactive gas preferably removes (desorbs) at least a portion of the functional groups formed on wafer 200 in step B from the first layer through a chemical reaction. The removed functional groups are exhausted from processing chamber 201. As a result, the second layer becomes a layer with fewer impurities than the first layer formed in step C. For example, as the reaction gas, a gas containing a reducing gas, an oxidizing gas, a nitriding gas, a sulfiding gas, a seleniding gas, a telluride gas, etc. can be used. As the reaction gas, one or more of these can be used. As the reducing gas, for example, a gas containing hydrogen (H 2) Gas, deuterium (D 2) Gas, Borane (BH 3) Gas, diborane (B 2H 6) Gas, carbon monoxide (CO) gas, ammonia (NH 3) Gas, monosilane (SiH 4) Gas, disilane (Si 2H 6) Gas, trisilane (Si 3H 8) Gas, monogermane (GeH 4) Gas, digermane (Ge 2H 6) and the like. In addition, as the reaction gas, for example, an oxidizing gas containing oxygen (O) gas can be used. As the oxidizing gas, for example, an oxidizing gas containing oxygen (O) gas can be used. 2) Ozone (O 3) Water vapor (H 2O), H 2 and O 2 mixed gas, hydrogen peroxide (H 2O 2) Nitrous oxide (N As the nitriding gas, for example, ammonia (NH 3) Gas, diazene (N 2H 2) Gas, hydrazine (N 2H 4) Gas, N 3H As the sulfide gas, for example, hydrogen sulfide (H 2S), dihydrogen disulfide (H 2S 2) Diammonium sulfide ((NH 4) 2S), dimethyl sulfide ((CH 3) 2S) and the like. As the sulfiding gas, one or more of these can be used. As the selenization gas, for example, a gas containing hydrogen selenide (H 2Se), diselenide (H 2Se 2) Dimethylselenide ((CH 3) 2Se) and the like. As the selenization gas, one or more of these can be used. As the tellurization gas, for example, a gas containing hydrogen telluride (H 2Te), hydrogen ditelluride (H 2Te 2) Dimethyltellurium ((CH 3) As the telluride gas, one or more of these can be used. After the first layer formed on the surface of wafer 200 (the inner surface of the recess) is transformed into the second layer, valve 243c is closed, and the supply of the reaction gas into the processing chamber 201 is stopped. Then, the processing chamber 201 is evacuated to remove gaseous substances and the like remaining therein. At this time, valves 243f to 243h are opened, and an inert gas is supplied into the processing chamber 201 via nozzles 249a to 249c. The inert gas supplied from nozzles 249a to 249c acts as a purge gas, thereby purging (flushing) the space in which wafer 200 is located, i.e., the interior of the processing chamber 201. [Predetermined Number of Implementations] By performing the first cycle of steps A to D described above non-simultaneously, i.e., asynchronously, n times (n is an integer greater than or equal to 1 or 2), a film having a desired composition can be formed on the surface of wafer 200 (the inner surface of the recess). For example, when a silane-based gas is used as the first source gas and a nitride gas is used as the reaction gas, a silicon nitride film (SiN film) is formed on the surface of wafer 200. It is preferred that the thickness of the second layer formed in each cycle be thinner than the desired film thickness, and that the above cycle be repeated multiple times until the film thickness formed by laminating the second layer reaches the desired film thickness. This can further uniformize the thickness of the film formed within the recess. For example, when the reaction gas is a reducing gas, a film mainly composed of the first element and the second element can be formed on the wafer 200. For example, when any one of an oxidizing gas, a nitride gas, a sulfide gas, a selenide gas, and a telluride gas is used as the reaction 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, and a telluride film containing the first element and the second element can be formed on the wafer 200. (Post-Purge and Atmospheric Pressure Restoration) After film formation is completed, an inert gas is supplied from nozzles 249a-249c into process chamber 201 as a purge gas, and exhaust is conducted from exhaust port 231a. This purges the interior of process chamber 201, removing any remaining gases, reaction byproducts, and the like (post-purge). The atmosphere within process chamber 201 is then replaced with an inert gas (inert gas replacement), and the pressure within process chamber 201 is restored to normal pressure (atmospheric pressure restoration). (Wafer Boat Unloading and Wafer Removal) Afterwards, the sealing cap 219 is lowered by the boat elevator 115, opening the lower end of the manifold 209. The processed wafers 200, supported by the boat 217, are then unloaded from the lower end of the manifold 209 to the exterior of the reaction tube 203 (boat unloading). After the boat is unloaded, the shutter 219s moves, sealing the lower end opening of the manifold 209 with the shutter 219s via the O-ring 220c (shutter closing). After being unloaded to the exterior of the reaction tube 203, the processed wafers 200 are removed from the boat 217 (wafer unloading). (3) Effects of this aspect According to this aspect, one or more of the following effects can be obtained. (a) In steps A and B, respectively, a first source gas and a first adsorption-inhibiting gas are supplied to wafer 200 to form functional groups that inhibit the adsorption of a second source gas. Then, in at least a portion of step C, a second source gas is supplied to wafer 200 to form a layer containing the first and second elements. This reduces the difference in the amount of second source gas adsorbed between the opening and the deep side, that is, reduces the variation in the concentration of the second element in the film within the recessed portion. Consequently, the uniformity of the film formed on the surface of wafer 200 can be improved. This is described below. Gas supplied to wafer 200 having recessed portions tends to be more readily absorbed by the opening side than by the deep portion. Therefore, in step C, the second source gas is more absorbed by the opening side than by the deep portion. As a result, the uniformity of the film formed on the surface of wafer 200 may be reduced. In this embodiment, in steps A and B, the first raw material gas and the first adsorption-inhibiting gas are respectively supplied to the wafer 200. After the functional groups that hinder the adsorption of the second raw material gas are formed on the wafer 200, the second raw material gas is supplied to the wafer 200 in step C to form a layer containing the first element and the second element. That is, before starting step C, the functional groups that hinder the adsorption of the second raw material gas are more on the opening side than on the deep side. Therefore, the adsorption of the second raw material gas can be suppressed on the opening side, and it is difficult to suppress the adsorption of the second raw material gas on the deep side. Thereby, the difference in the adsorption amount of the second raw material gas between the opening side and the deep side can be reduced. As a result, the uniformity of the film formed on the surface of the wafer can be improved. (b) The amount of the second source gas adsorbed on the deep side is preferably greater than the amount of the first adsorption-inhibiting gas. This makes it difficult to inhibit the adsorption of the second source gas on the deep side, while it is possible to inhibit the adsorption of the second source gas on the open side. This further reduces the difference in the amount of the second source gas adsorbed between the open side and the deep side. (c) It is preferable to make the exposure amount of the second source gas greater than the exposure amount of the first adsorption-inhibiting gas. This allows the amount of the second source gas adsorbed on the deep side to be greater than the amount of the first adsorption-inhibiting gas adsorbed on the deep side. This further reduces the difference in the amount of the second source gas adsorbed between the open side and the deep side. In addition, it is preferred that at least one of the following 1 to 6 is satisfied. In this way, the exposure amount of the second raw material gas can be made greater than the exposure amount of the first adsorption inhibiting gas. 1. The second raw material gas supply time in step C is made longer than the first adsorption inhibiting gas supply time in step B. 2. The process pressure in step C is made higher than the process pressure in step B. 3. The second raw material gas supply flow rate in step C is made greater than the first adsorption inhibiting gas supply flow rate in step B. 4. The inert gas supply flow rate in step C is made less than the inert gas supply flow rate in step B. 5. The partial pressure of the second raw material gas in the process chamber 201 in step C is made higher than the partial pressure of the first adsorption inhibiting gas in the process chamber 201 in step B. 6. The molar fraction of the second raw material gas in the gas in the process chamber 201 in step C is made greater than the molar fraction of the first adsorption inhibiting gas in step B. (d) The amount of the first adsorption-inhibiting gas adsorbed on the deep side is preferably smaller than the amount of the first source gas. In this case, adsorption of the second source gas is less inhibited on the deep side, while adsorption of the second source gas can be inhibited on the open side. This further reduces the difference in the amount of the second source gas adsorbed between the open side and the deep side. (e) By making the exposure amount of the first adsorption-inhibiting gas smaller than the exposure amount of the first source gas, the amount of the first adsorption-inhibiting gas adsorbed on the deep side can be reduced compared to the amount of the first source gas adsorbed on the deep side, which is preferable. In this case, adsorption of the second source gas is less likely to be suppressed on the deep side, while adsorption of the second source gas can be suppressed on the open side. As a result, the difference in the amount of the second source gas adsorbed between the open side and the deep side can be further reduced. Furthermore, it is preferred that at least one of the following items 7 to 12 be satisfied. This allows the exposure amount of the first adsorption inhibitory gas to be less than the exposure amount of the first source gas. 7. The first adsorption inhibitory gas supply time in step B is shorter than the first source gas supply time in step A. 8. The process pressure in step B is lower than the process pressure in step A. 9. The first adsorption inhibitory gas supply flow rate in step B is less than the first source gas supply flow rate in step A. 10. The inert gas supply flow rate in step B is greater than the inert gas supply flow rate in step A. 11. The partial pressure of the first adsorption inhibitory gas in the process chamber 201 in step B is lower than the partial pressure of the first source gas in the process chamber 201 in step A. 12. The molar fraction of the first adsorption inhibitory gas in the gas in the process chamber 201 in step B is less than the molar fraction of the first source gas in the gas in the process chamber 201 in step A. (f) As described above, in step B, the amount of the first adsorption-inhibiting gas adsorbed on the opening side is preferably greater than that on the deep side. Therefore, the first adsorption-inhibiting gas preferably does not contain the first element. This allows a layer containing a uniform amount of the first element to be formed throughout the entire recess. (g) The reaction gas preferably removes the functional groups (functional groups derived from the first adsorption inhibiting gas) formed on the wafer 200 in step B through a chemical reaction. This can suppress degradation of film properties caused by absorption of elements derived from the first adsorption inhibiting gas into the film. (h) When the amount of the second element in the layer formed by the above cycle is less than the amount of the first element, the concentration of the second element in the film within the recessed portion is likely to vary greatly due to differences in the amount of the second source gas adsorbed within the recessed portion. Even in such a situation, the technique of the present invention can reliably reduce the concentration variation of the second element in the film within the recessed portion. This can reliably improve the uniformity of the film formed on the surface of wafer 200. (i) By controlling the amount of the second source gas adsorbed on wafer 200 according to the processing conditions of step A, the concentration of the second element in the film or layer can be controlled. Specifically, by adjusting the processing conditions of step A by controlling, for example, the amount of the first source gas supplied to wafer 200, the amount of the second source gas adsorbed on wafer 200 is controlled, thereby controlling the concentration of the second element in the film or layer. (j) The molecular radius of the first adsorption-inhibiting gas is preferably smaller than that of the first source gas. This makes it less likely that the functional groups formed on wafer 200 in step A will inhibit the adsorption of the first adsorption-inhibiting gas on wafer 200. Consequently, the concentration variation of the second element in the film within the recessed portion can be further reduced, and as a result, the uniformity of the film formed on the surface of wafer 200 can be reliably improved. (k) In the case where a hydrophilic functional group is formed on the wafer 200 in step A and step B, it is preferred that the second raw material gas supplied in step C is a hydrophilic gas. For example, in the case where a chlorosilane-based gas is supplied to the wafer 200 in step A and a gas containing Cl is supplied to the wafer 200 in step B, a hydrophilic Cl group (functional group) is formed on the wafer 200. In this case, in step C, it is preferred that a gas containing a second element and a halogen element is supplied to the wafer 200 as the hydrophilic second raw material gas. In addition, in the case where a hydrophobic functional group is formed on the wafer 200 in step A and step B, it is preferred that the second raw material gas supplied in step C is a hydrophobic gas. For example, in the case where an aminosilane-based gas is supplied to the wafer 200 in step A and a gas containing an alkyl group is supplied to the wafer 200 in step B, a hydrophobic alkyl group (functional group) is formed on the wafer 200. In this case, in step C, it is preferred to supply a gas containing, for example, a second element and an organic ligand as a hydrophobic second source gas to wafer 200. In this case, the functional groups formed on wafer 200 in steps A and B easily inhibit the adsorption of the second source gas onto wafer 200. Therefore, it is possible to reliably reduce the variation in the concentration of the second element in the film within the recessed portion, and as a result, it is possible to reliably improve the uniformity of the film formed on the surface of wafer 200. Furthermore, the reactivity of nitriding gas with respect to the bond between an atom and a halogen group tends to be higher than the reactivity of nitriding gas with respect to the bond between an atom and an organic ligand. Therefore, for example, when the reactive gas is a nitriding gas and a layer or film containing a first element, a second element, and N is formed, it is preferable that the first source gas, the first adsorption-inhibiting gas, and the first source gas contain a halogen group in their molecular structure. This can reduce the likelihood of impurities derived from the organic ligand being present in the second layer or film. (1) The above-mentioned effects can also be obtained when a predetermined substance (gaseous substance, liquid substance) is arbitrarily selected and used from the various raw material gases, various adsorption-inhibiting gases, various reaction gases, and various inert gases. (4) Modifications The processing sequence in this aspect can be modified as shown in the following modifications. These modifications can be combined arbitrarily. Unless otherwise specified, the processing procedures and processing conditions in each step of each modification can be set to be the same as the processing procedures and processing conditions in each step of the above-mentioned processing sequence. (Variant 1) As in the processing sequence shown in FIG. 6(a) and below, the execution period of step B and the execution period of step C may be repeated, and after step A is performed, steps B and C are performed simultaneously, and then step D is performed. Alternatively, as in the processing sequence shown in FIG. 6(b) and below, the execution period of step B and a portion of the execution period of step C may be repeated, and steps A, B, C, and D may be performed in sequence. Alternatively, as in the processing sequence shown in FIG. 6(c) and below, the execution period of step B and the execution period of step C may be continuous, and steps A, B, C, and D may be performed in sequence. Alternatively, as in the processing sequence shown in FIG. 6(d) and below, the entire execution period of step B and a portion of the execution period of step C may be repeated, and steps A, C, B, and D may be performed in that order. (first raw material gas → first adsorption barrier gas + second raw material gas → reaction gas) × n (first raw material gas → first adsorption barrier gas → first adsorption barrier gas + second raw material gas → second raw material gas → reaction gas) × n (first raw material gas → first adsorption barrier gas | second raw material gas → reaction gas) × n (first raw material gas → second raw material gas → first adsorption barrier gas + second raw material gas → reaction gas) × n In this specification, the "|" in the above "first adsorption barrier gas | second raw material gas" indicates that a flushing process is not performed on the processing chamber 201. It is preferable that the first adsorption barrier gas and the second raw material gas are gases that do not react with each other. In this modification, the same effect as in the above-described embodiment can be obtained. In this modification, the cycle time can be further shortened, thereby improving the productivity of the film forming process. In addition, in the processing sequence shown in FIG. 6( d ) and below, the second raw material gas is supplied to the wafer 200 adsorbed with the first raw material gas and the first adsorption barrier gas only in a portion of step C. Even in this case, the same effect as in the above-described embodiment can be obtained. That is, it is preferable that the second raw material gas is supplied to the wafer 200 adsorbed with the first raw material gas and the first adsorption barrier gas only in at least a portion of step C. (Variant 2) Alternatively, during at least a portion of step A, the first source gas may be supplied to the wafer 200 on which the first adsorption-inhibiting gas is adsorbed. Specifically, as in the process sequence shown in FIG7(a) and below, after the step of supplying the first adsorption-inhibiting gas to the wafer 200 is performed, steps A, C, B, and D may be performed in sequence. Alternatively, as in the process sequence shown in FIG7(b) and below, the entire execution period of step A may be overlapped with a portion of the execution period of step B, and the steps may be performed in the order of steps B, A, C, and D. Alternatively, as in the process sequence shown in FIG7(c) and below, the execution periods of steps A, B, and C may be overlapped, and steps A, B, and C may be performed simultaneously, followed by step D. Alternatively, as in the process sequence shown in FIG7(d) and below, a portion of the execution period of step A may be overlapped with the entire execution period of steps B and C, and after starting step A, steps B and C may be performed simultaneously, followed by step D. (first adsorption barrier gas → first source gas → first adsorption barrier gas → second source gas → reaction gas) × n (first adsorption barrier gas → first adsorption barrier gas + first source gas → first adsorption barrier gas → second source gas → reaction gas) × n (first source gas + first adsorption barrier gas + second source gas → reaction gas) × n (first source gas → first source gas + first adsorption barrier gas + second source gas → first source gas → reaction gas) × n This modification also achieves the same effects as the above-described embodiment. This modification further reduces the difference in the amount of adsorbed first source gas between the opening side and the deep side. Consequently, the uniformity of the film within the recess can be improved. (Variation 3) The process may further include step E of supplying a second adsorption inhibitor gas different from the first adsorption inhibitor gas to wafer 200, and supplying the first source gas to wafer 200 adsorbed with the second adsorption inhibitor gas during at least a portion of step A. Specifically, the process may be performed in the order of steps E, A, B, C, and D, as shown in FIG8 and the following processing sequence. (second adsorption inhibitory gas → first source gas → first adsorption inhibitory gas → second source gas → reaction gas) × n As the second adsorption inhibiting gas, for example, one or more of the gases listed as examples of the first raw material gas can be used. In step E, the second adsorption-inhibiting gas is supplied to the wafer 200 in the processing chamber 201 by the second adsorption-inhibiting gas supply system. As the processing conditions when supplying the second adsorption inhibitory gas in this step, the following are exemplified: processing temperature: 350~700℃, preferably 500~600℃, processing pressure: 1~10000Pa, preferably 10~1333Pa, second adsorption inhibitory gas supply flow rate: 0.01~3slm, preferably 0.1~1slm, second adsorption inhibitory gas supply time: 10~120 seconds, preferably 20~60 seconds, inert gas supply flow rate (for each gas supply pipe): 0~10slm is exemplified. By supplying the second adsorption-inhibiting gas to the wafer 200 under the aforementioned processing conditions, the second adsorption-inhibiting gas can be adsorbed onto adsorption sites on the surface of the wafer 200. By supplying the second adsorption-inhibiting gas to the wafer 200 under the aforementioned processing conditions, the adsorption of the first source gas supplied in step A onto the wafer 200 can be inhibited. When hydrophilic functional groups are formed on the wafer 200 in steps A, B, and E, a hydrophilic gas is preferably used as the second source gas in step C. Alternatively, when hydrophobic functional groups are formed on the wafer 200 in steps A, B, and E, a hydrophobic gas is preferably used as the second source gas in step C. This modification also achieves the same effects as the above-described embodiment. This modification further reduces the difference in the amount of adsorbed first source gas between the opening side and the deep side. Consequently, the uniformity of the film within the recess can be improved. Furthermore, in Modification 3, when hydrophilic functional groups are formed on wafer 200 in steps A, B, and E, when a hydrophilic second source gas is supplied, the hydrophilic functional groups tend to inhibit adsorption of the second source gas onto wafer 200. Similarly, when hydrophobic functional groups are formed on wafer 200 in steps A, B, and E, when a hydrophobic second source gas is supplied, the hydrophobic functional groups tend to inhibit adsorption of the second source gas onto wafer 200. This reliably reduces variations in the concentration of the second element in the film within the recessed portion, and as a result, reliably improves the uniformity of the film formed on the surface of wafer 200. (Variant 4) A second loop including step A and step D but not including step B may be further provided. Specifically, as in the processing sequence shown in FIG9 and below, after a first loop in which steps A to D are non-simultaneously performed in the order of steps A, B, C, and D for a predetermined number of times (n times, where n is an integer of 1 or 2 or greater), a second loop including steps A and step D but not including step B may be performed a predetermined number of times (m times, where m is an integer of 1 or 2 or greater). (first source gas → first adsorption inhibiting gas → second source gas → reaction gas) × n → (first source gas → reaction gas) × m This variation also achieves the same effects as the above-described embodiment. In this variation, a film can be formed by laminating a layer containing the first element and the second element with a layer containing the first element. This allows for more detailed control of the concentration of the second element in the film, even when forming a film with a low concentration of the second element. <Other aspects of the present invention> While aspects of the present invention have been specifically described above, the present invention is not limited to the above aspects and various modifications can be made without departing from the spirit and scope of the present invention. For example, in the above aspects, a gas that does not contain the first element is used as the first adsorption-inhibiting gas. However, the present invention is not limited to this aspect. For example, a gas containing the first element may also be used as the first adsorption-inhibiting gas. In this case, at least some of the effects of the above aspects can also be achieved. For example, in the above-mentioned aspect, as the hydrophilic functional group formed on the wafer 200 in step A and step B, a halogen group is used as an example for explanation, and as the hydrophobic functional group, an alkyl group is used as an example for explanation. However, the present invention is not limited to such an aspect. For example, the hydrophilic functional group formed on the wafer 200 in step A and step B can be an alkoxide group, an amine group, etc., and the hydrophobic functional group can be a hydrogen group, a cycloalkyl group, a phenyl group, a cyclopentadienyl group, etc. As the first raw material gas and the first adsorption-impeding gas, as the hydrophilic functional group, a gas having an alkoxide group, an amine group, etc. can be appropriately used, and as the hydrophobic functional group, a gas having a cycloalkyl group, a phenyl group, a cyclopentadienyl group, etc. can be appropriately used. In such cases, the same effect as the above-mentioned aspect can also be obtained. For example, in the above-described embodiment, a gas having a halogen group is used as an example of a hydrophilic second raw material gas, and a gas having an alkyl group or a hydrogen group is used as an example of a hydrophobic second raw material gas. However, the present invention is not limited to such an embodiment. For example, a gas having an alkoxide group or an amine group can be used as a hydrophilic second raw material gas, and a gas having a cycloalkyl group, a phenyl group, a cyclopentadienyl group, etc. can be used as a hydrophobic second raw material gas. The recipe used in each process is preferably prepared individually according to the process content, recorded and stored in the memory device 121c via a telecommunication line or external memory device 123. Furthermore, when each process is started, the CPU 121a preferably selects an appropriate recipe from the multiple recipes recorded and stored in the memory device 121c based on the process content. This allows films of various film types, composition ratios, film qualities, and film thicknesses to be formed with high reproducibility using a single substrate processing apparatus. This also reduces the burden on operators, prevents operational errors, and allows each process to be started quickly. The above recipes are not limited to newly created ones; for example, they can be prepared by modifying an existing recipe already installed in a substrate processing apparatus. When modifying a recipe, the modified recipe can be installed in the substrate processing apparatus via a telecommunications line or a recording medium containing the recipe. Alternatively, the input / output device 122 of an existing substrate processing apparatus can be used to directly modify an existing recipe installed in the apparatus. In the above-mentioned aspect, an example of forming a film using a batch-type substrate processing device that processes multiple substrates at a time is described. The present invention is not limited to the above-mentioned aspect, and for example, it can also be appropriately applied when forming a film using a single-piece substrate processing device that processes one or several substrates at a time. In addition, in the above-mentioned aspect, an example of forming a film using a substrate processing device having a hot-wall type processing furnace is described. The present invention is not limited to the above-mentioned aspect, and it can also be appropriately applied when forming a film using a substrate processing device having a cold-wall type processing furnace. In addition, in the above-mentioned aspect, an example of activating a gas by heat is described. However, the present invention is not limited thereto. For example, it can also be appropriately applied when activating a gas by plasma generated inside or outside the processing chamber 201, or when activating a gas by irradiating an electromagnetic wave to the gas using a lamp or the like. When these substrate processing apparatuses are used, each process can be performed using the same processing procedures and processing conditions as those in the above-described aspects or modifications, and the same effects as those in the above-described aspects or modifications can be obtained. The above-mentioned aspects or modifications can be used in combination as appropriate. The processing procedures and processing conditions in this case can be, for example, the same as those in the above-mentioned aspects or modifications. 115: Wafer boat elevator 115s: Shutter opening and closing mechanism 121: Controller 121a: CPU 121b: RAM 121c: Memory device 121d: I / O port 121e: Internal bus 122: Input / output device 123: External memory device 200: Wafer (substrate) 201: Processing chamber 202: Processing furnace 203: Reaction tube 207: Heater 209: Manifold 217: Wafer boat 218: Heat shield 219: Sealing cover 219s: Shutter 220a, 220b, 220c: O-ring 231: Exhaust pipe 231a: Exhaust port 232a-232h: Gas supply pipes 241a-241h: Mass flow controller (MFC) 243a~243h: Valve 244: APC valve 245: Pressure sensor 246: Vacuum pump 248: Accumulated supply system 249a, 249b, 249c: Nozzle 250a, 250b, 250c: Gas supply hole 255: Rotating shaft 263: Temperature sensor 267: Rotating mechanism FIG1 is a schematic diagram of the vertical processing furnace of a substrate processing apparatus, and shows a portion of the processing furnace 202 in a longitudinal cross-sectional view. FIG2 is a schematic diagram of the vertical processing furnace of a substrate processing apparatus, and shows a portion of the processing furnace 202 in a cross-sectional view taken along line AA of FIG1 . FIG3 is a schematic diagram of the controller 121 of the substrate processing apparatus, and shows a control system of the controller 121 in a block diagram. FIG4 is a diagram illustrating a processing sequence according to one embodiment of the present invention. FIG5(a) is a partially enlarged cross-sectional view of the surface of a wafer 200 adsorbed with a first source gas. FIG5(b) is a partially enlarged cross-sectional view of the surface of a wafer 200 adsorbed with a first source gas and a first adsorption barrier gas. FIG5(c) is a partially enlarged cross-sectional view of the surface of a wafer 200 adsorbed with a first source gas, a first adsorption barrier gas, and a second source gas. FIG6(a) is a diagram illustrating an example of a processing sequence according to Modification 1. FIG6(b) is a diagram illustrating an example of a processing sequence according to Modification 1. Figure 6(c) is a diagram showing an example of the processing sequence in Modification 1. Figure 6(d) is a diagram showing an example of the processing sequence in Modification 1. Figure 7(a) is a diagram showing an example of the processing sequence in Modification 2. Figure 7(b) is a diagram showing an example of the processing sequence in Modification 2. Figure 7(c) is a diagram showing an example of the processing sequence in Modification 2. Figure 7(d) is a diagram showing an example of the processing sequence in Modification 2. Figure 8 is a diagram showing the processing sequence in Modification 3. Figure 9 is a diagram showing the processing sequence in Modification 4.

Claims

1. A substrate processing method comprising performing the following steps (a) to (d) to form a layer comprising a first element and a second element: (a) supplying a first raw material gas having silicon, tungsten, titanium, molybdenum, tantalum, cobalt, yttrium, ruthenium, hafnium, zirconium, aluminum, boron, gallium, indium, phosphorus, or carbon, i.e., the first element, to a substrate having a recess on its surface; (b) supplying a first adsorption barrier gas to the substrate; (c) supplying a second raw material gas having a second element selected from silicon, tungsten, titanium, molybdenum, tantalum, cobalt, yttrium, ruthenium, hafnium, zirconium, aluminum, boron, gallium, indium, phosphorus, or carbon, and different from the first element, to the substrate; and (d) supplying a reaction gas to the substrate; wherein functional groups formed on the substrate in (a) and (b) prevent the adsorption of the second raw material gas onto the substrate; and in at least a portion of (c), supplying the second raw material gas to the substrate having adsorbed the first raw material gas and the first adsorption barrier gas.

2. The substrate processing method as described in claim 1, wherein, The amount of the second raw material gas adsorbed on the deep side of the above-mentioned concave portion is greater than the amount of the first adsorption-blocking gas.

3. The substrate processing method as described in claim 2, wherein, The exposure amount of the second raw material gas is greater than the exposure amount of the first adsorption barrier gas.

4. The substrate processing method as described in claim 1, wherein, The amount of the first adsorption-blocking gas adsorbed on the deep side of the above-mentioned concave portion is less than the amount of the first raw material gas.

5. The substrate processing method as described in claim 4, wherein, The exposure amount of the first adsorption barrier gas is made less than the exposure amount of the first raw material gas.

6. The substrate processing method as described in any of claims 1 to 5, wherein, The first adsorption barrier gas mentioned above does not contain the first element mentioned above.

7. The substrate processing method as described in any of claims 1 to 5, wherein, The aforementioned reactive gas removes the functional groups formed on the substrate in (b) through a chemical reaction.

8. The substrate processing method according to any one of claims 1 to 5, wherein, The number of the second element in the layer formed by the first cycle is less than the number of the first element.

9. The substrate processing method as described in any of claims 1 to 5, wherein, The amount of the second raw material gas adsorbed on the substrate is controlled by the processing conditions in (a).

10. The substrate processing method according to any one of claims 1 to 5, wherein, The molecular radius of the first adsorption hindering gas is smaller than the molecular radius of the first raw material gas.

11. The substrate processing method according to any one of claims 1 to 5, wherein, The following (i) or (ii) holds true: (i) a hydrophilic functional group is formed on the substrate in (a) and (b), and the second raw material gas system is a hydrophilic gas; (ii) a hydrophobic functional group is formed on the substrate in (a) and (b), and the second raw material gas system is a hydrophobic gas.

12. The substrate processing method according to any one of claims 1 to 5, wherein, In at least a portion of (a), the first raw material gas is supplied to the substrate on which the first adsorption barrier gas is adsorbed.

13. The substrate processing method according to any one of claims 1 to 5, further comprising: (e) The step of supplying the substrate with a second adsorption barrier gas that is different from the first adsorption barrier gas; and, in at least a portion of (a), the first raw material gas is supplied to the substrate on which the second adsorption barrier gas is adsorbed.

14. The substrate processing method as described in claim 13, wherein, The following (i) or (ii) holds true: (i) a hydrophilic functional group is formed on the substrate in (a), (b) and (e), and the second raw material gas system is a hydrophilic gas; (ii) a hydrophobic functional group is formed on the substrate in (a), (b) and (e), and the second raw material gas system is a hydrophobic gas.

15. The substrate processing method of any one of claims 1 to 5, further comprising a second cycle, wherein the second cycle includes (a) and (d) but not (b).

16. The substrate processing method according to any one of claims 1 to 5, wherein, The above-mentioned reactant gas is a nitriding gas, and the above-mentioned first raw material gas, the above-mentioned first adsorption barrier gas and the above-mentioned first raw material gas contain halogen elements in their molecular structure.

17. The substrate processing method according to any one of claims 1 to 5, wherein, The aforementioned reaction gases are one or more of the following: reducing gas, oxidizing gas, nitriding gas, sulfiding gas, selenizing gas, and tellurizing gas.

18. A method for manufacturing a semiconductor device, comprising performing the following steps (a) to (d) to form a layer comprising a first element and a second element: (a) supplying a first raw material gas having silicon, tungsten, titanium, molybdenum, tantalum, cobalt, yttrium, ruthenium, hafnium, zirconium, aluminum, boron, gallium, indium, phosphorus, or carbon (i.e., the first element) to a substrate having recesses on its surface; (b) supplying a first adsorption barrier gas to the substrate; (c) supplying a second raw material gas having a second element selected from silicon, tungsten, titanium, molybdenum, tantalum, cobalt, yttrium, ruthenium, hafnium, zirconium, aluminum, boron, gallium, indium, phosphorus, or carbon, and different from the first element, to the substrate; and (d) supplying a reactant gas to the substrate; and wherein, in (a) and (b), functional groups formed on the substrate prevent the adsorption of the second raw material gas onto the substrate. In at least a portion of (c), the second raw material gas is supplied to the substrate that has adsorbed the first raw material gas and the first adsorption barrier gas.

19. A substrate processing apparatus comprising: a first raw material gas supply system for supplying a first raw material gas having silicon, tungsten, titanium, molybdenum, tantalum, cobalt, yttrium, ruthenium, hafnium, zirconium, aluminum, boron, gallium, indium, phosphorus, or carbon, i.e., a first element; a first adsorption-blocking gas supply system for supplying a first adsorption-blocking gas; a second raw material gas supply system for supplying a second raw material gas having a second element selected from silicon, tungsten, titanium, molybdenum, tantalum, cobalt, yttrium, ruthenium, hafnium, zirconium, aluminum, boron, gallium, indium, phosphorus, or carbon, and different from the first element; a reaction gas supply system for supplying a reaction gas; and a control unit configured to control the first raw material gas supply system, the first adsorption-blocking gas supply system, the second raw material gas supply system, and the reaction gas supply system to perform the following processing: the processing includes performing the following steps (a) to (d), forming a first cycle containing the first element and the second element. (a) A process of supplying the first raw material gas to a substrate having a recess on its surface; (b) A process of supplying the first adsorption barrier gas to the substrate; (c) A process of supplying the second raw material gas to the substrate; (d) A process of supplying the reactant gas to the substrate; wherein, in (a) and (b), functional groups formed on the substrate prevent the adsorption of the second raw material gas onto the substrate; and in at least a portion of (c), the second raw material gas is supplied to the substrate on which the first raw material gas and the first adsorption barrier gas are adsorbed.

20. A program for executing a program using a computer on a substrate processing apparatus: The program includes performing the following steps (a) to (d) to form a first cycle comprising a layer containing a first element and a second element: (a) supplying a first raw material gas having silicon, tungsten, titanium, molybdenum, tantalum, cobalt, yttrium, ruthenium, hafnium, zirconium, aluminum, boron, gallium, indium, phosphorus, or carbon (i.e., the first element) to a substrate having recesses on its surface; (b) supplying a first adsorption barrier gas to the substrate; (c) supplying a second raw material gas having a second element selected from silicon, tungsten, titanium, molybdenum, tantalum, cobalt, yttrium, ruthenium, hafnium, zirconium, aluminum, boron, gallium, indium, phosphorus, or carbon, and different from the first element, to the substrate; (d) supplying a reactant gas to the substrate; and, in (a) and (b), functional groups formed on the substrate prevent the adsorption of the second raw material gas onto the substrate. In at least a portion of (c), the second raw material gas is supplied to the substrate that has adsorbed the first raw material gas and the first adsorption barrier gas.

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