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

Abstract

The objective of this invention is to provide a technique that allows a specific surface on a substrate to preferentially form a film compared to other surfaces. The substrate processing method of this invention involves performing a first cycle a first number of times to form a film containing a first element on at least a portion of the substrate. The first cycle is performed non-simultaneously: (a1) supplying a first gas containing the first element to a substrate having a first surface and a second surface respectively composed of different substances, thereby forming a substance X containing the first element on at least a portion of the substrate; and (a2) supplying a first reactive gas to the substrate to react with substance X; and ensuring that the incubation time of the first gas on the second surface is longer than the incubation time on the first surface; and in (a1), removing at least a portion of the substance X formed on the substrate.

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 one of the steps in the manufacturing process of semiconductor devices or the substrate processing process, there is a process for preferentially forming a film on a specific surface of a substrate compared to other surfaces (for example, see Patent Document 1). [Prior Art Document] [Patent Document] [Patent Document 1] International Publication No. 2018 / 179354 (Problems that the invention aims to solve) The present invention provides a technology that allows a film to be formed preferentially on a specific surface of a substrate compared to other surfaces. (Technical Means for Solving the Problem) According to one aspect of the present invention, the following technology is provided: a first cycle is performed a first time to form a film containing a first element on at least a portion of a substrate, wherein the first cycle is performed non-simultaneously: (a1) a step of supplying a first gas containing the first element to a substrate having a first surface and a second surface each composed of different substances, and forming a substance X containing the first element on at least a portion of the substrate, and (a2) a step of supplying a first reaction gas that reacts with the substance X to the substrate; the incubation time of the first gas on the second surface is longer than the incubation time on the first surface; and in (a1), at least a portion of the substance X formed on the substrate is removed. (Compare to the efficacy of the prior art) According to the present invention, a film can be formed preferentially on a specific surface of a substrate compared to other surfaces. <One Aspect of the Invention> The following describes one aspect of the present invention primarily with reference to Figures 1 to 5 . The figures used in the following description are schematic, and the dimensional relationships and ratios of the elements shown in the figures do not necessarily correspond to actual dimensions. Furthermore, the dimensional relationships and ratios of the elements shown in multiple figures do not necessarily correspond to actual dimensions. (1) Configuration of Substrate Processing Apparatus As shown in FIG1 , a processing furnace 202 of the substrate processing apparatus includes a heater 207 as a heating unit (temperature adjustment unit). The heater 207 functions as an activation mechanism (excitation unit) that activates (excites) gas by heat. A reaction tube 203 is provided inside 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 top and an open bottom. A manifold 209 is provided below the reaction tube 203 to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing member. The processing vessel (reaction vessel) primarily comprises the reaction tube 203 and the manifold 209. Within the processing vessel is formed a processing chamber 201 capable of accommodating one or more wafers 200, which serve as substrates. In the processing chamber 201, nozzles 249a and 249b are respectively provided to penetrate the side wall of the manifold 209. The nozzles 249a and 249b are connected to the gas supply pipes (pipes) 232a and 232b respectively. Gas supply pipes 232a and 232b are provided, starting from the upstream side, with mass flow controllers (MFCs) 241a and 241b, respectively, as flow controllers (flow control units), and valves 243a and 243b, respectively, as on-off valves. Downstream of valves 243a and 243b, gas supply pipes 232c and 232d, respectively, for supplying inert gas, are connected to gas supply pipes 232a and 232b. MFCs 241c and 241d, respectively, and valves 243c and 243d, respectively, are provided on gas supply pipes 232c and 232d, starting from the upstream side. Nozzles 249a and 249b are positioned in the annular space between the inner wall of the reaction tube 203 and the wafers 200, extending upward from the bottom of the inner wall of the reaction tube 203. These nozzles 249a and 249b are positioned vertically along the inner wall of the reaction tube 203, extending upward in the direction in which the wafers 200 are loaded. Gas supply holes 250a and 250b are provided on the sides of the nozzles 249a and 249b, respectively, for supplying gas. These gas supply holes 250a and 250b open toward the center of the reaction tube 203 and supply gas toward the wafers 200. A plurality of gas supply holes 250a and 250b are provided, extending from the bottom of the reaction tube 203 to the top. A first gas containing a first element 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 first reaction gas that reacts with the substance containing the first element is supplied into the processing chamber 201 from the gas supply pipe 232 b via the MFC 241 b , the valve 243 b , and the nozzle 249 b . An inert gas is supplied into the processing chamber 201 from the gas supply pipes 232c and 232d via the MFCs 241c and 241d, valves 243c and 243d, the gas supply pipes 232a and 232b, the nozzles 249a and 249b, respectively. The first gas supply system is mainly composed of the gas supply pipe 232a, MFC241a, and valve 243a. The first reaction gas supply system is mainly composed of the gas supply pipe 232b, MFC241b, and valve 243b. The first gas supply system and the first reaction gas supply system can also be collectively referred to as the gas supply system. In addition, the inert gas supply system is mainly composed of the gas supply pipes 232c, 232d, MFC241c, 241d, and valves 243c, 243d. The inert gas supply system can also be included in the gas supply system. Any or all of the various supply systems described above may be configured as a centralized gas supply system 248, which integrates valves 243a-243d, MFCs 241a-241d, and the like. The centralized gas supply system 248 is connected to each of the gas supply pipes 232a-232d, and controls the supply of various gases into the gas supply pipes 232a-232d via the controller 121 (described later). Specifically, the opening and closing of the valves 243a-243d and the flow rate adjustment by the MFCs 241a-241d are controlled by the controller 121 (described later). An exhaust pipe 231 for exhausting the environment within the processing chamber 201 is provided in the reaction tube 203. The exhaust pipe 231 is connected to a vacuum pump 246 serving as a vacuum exhaust device via a pressure sensor 245 serving as a pressure detector (pressure detection unit) for detecting the pressure within the processing chamber 201, and an APC (Auto Pressure Controller) valve 244 serving as a pressure regulator (pressure regulation unit). The APC valve 244 is configured to enable and disable vacuum exhaust within the processing chamber 201 by opening and closing the valve depending on the state of the vacuum pump 246. Furthermore, the valve opening is adjusted based on the pressure information detected by the pressure sensor 245 when the vacuum pump 246 is in operation, thereby adjusting the pressure within the processing chamber 201. The exhaust system is primarily composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 can also be considered to be included in the exhaust system. Below the manifold 209, a sealing cover 219 is provided, serving as a furnace port cover that hermetically seals the lower opening of the manifold 209. An O-ring 220b is provided on the upper surface of the sealing cover 219, serving as a sealing member that abuts the lower end of the manifold 209. Below the sealing cover 219, a rotating mechanism 267 is provided for rotating the wafer boat 217, described later. A rotating shaft 255 of the rotating mechanism 267 passes through the sealing cover 219 and is connected to the wafer boat 217. The wafer boat elevator 115 is configured to move the wafer boat 217 into and out of the processing chamber 201 by raising and lowering the sealing cover 219. The wafer boat elevator 115 serves as a transport device (transport mechanism) that transports the wafer boat 217, or wafers 200, into and out of the processing chamber 201. The wafer boat 217, serving as a substrate support, is configured to support multiple wafers, for example, 25 to 200 wafers 200, in a horizontal position with their centers aligned vertically in multiple stages, i.e., arranged at intervals. The wafer boat 217 is made of a heat-resistant material such as quartz or SiC. Heat insulation plates 218, also made of a heat-resistant material such as quartz or SiC, are supported in multiple stages at the bottom of the wafer boat 217. In this specification, numerical ranges such as "25 to 200 wafers" are intended to include both lower and upper limits. Therefore, for example, "25 to 200 wafers" means "25 or more and 200 or less." The same applies to other numerical ranges. A temperature sensor 263 is installed within the reaction tube 203 as a temperature detector. The power supply to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, thereby achieving the desired temperature distribution within the processing chamber 201. The temperature sensor 263 is L-shaped and located along the inner wall of the reaction tube 203. As shown in FIG2 , the control unit (control means), i.e., the controller 121, is composed of a computer and includes a CPU (Central Processing Unit) 121a, a RAM (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 exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, such as a touch panel, is connected to the controller 121. Furthermore, the substrate processing apparatus may be configured to include one control unit or to include multiple control units. That is, one control unit or multiple control units may be used to control the processing sequence described below. Furthermore, the multiple control units may be configured as a control system interconnected by a wired or wireless communication network, or the control system as a whole may be used to control the processing sequence described below. When the term "control unit" is used in this specification, it means a case where one control unit is included, a case where a plurality of control units are included, or a case where a control system composed of a plurality of control units is included. The memory device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), etc. The control program for controlling the operation of the substrate processing device 100, or the process recipe that records the procedures or conditions for the substrate processing described later, etc., can be readable and stored in the memory device 121c. The process recipe functions as a program, which is a combination of the various programs in the substrate processing described later executed by the controller 121 to obtain a predetermined result. Hereinafter, the general term for process recipes, control programs, etc. is also referred to as a program. In addition, the process recipe is also referred to as a recipe. When the word program is used in this specification, it refers to the case of only the recipe itself, the case of only the control program itself, or the case of both. RAM 121b is a memory area (working area) configured to temporarily store the program or data read out by the CPU 121a. The I / O port 121d is connected to the MFCs 241a to 241d, valves 243a to 243d, pressure sensor 245, APC valve 244, vacuum pump 246, heater 207, temperature sensor 263, rotation mechanism 267, boat elevator 115, 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 in response to input of an operation command from the input / output device 122. Based on the contents of the read recipe, the CPU 121a is configured to control the flow rate adjustment of various gases using the MFCs 241a to 241d, the opening and closing of the valves 243a to 243d, the opening and closing of the APC valve 244 and the pressure adjustment performed by the APC valve 244 using the pressure sensor 245, the activation and deactivation 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, and the elevation of the wafer boat 217 by the boat elevator 115. The controller 121 can be constructed by installing the above-mentioned program recorded by an external memory device (such as a magnetic disk such as a hard disk, an optical disk such as a CD, a magneto-optical disk such as an MO, a semiconductor memory such as a USB memory) 123 into a computer. The memory device 121c or the external memory device 123 is constructed as a recording medium that can be read by a computer. Hereinafter, as a general term, these are referred to as recording media. When the term recording medium is used in this specification, it refers to the case where only the memory device 121c is included, the case where only the external memory device 123 is included, or the case where both are included. Moreover, the provision of programs to the computer can also be carried out without using the external memory device 123, but using communication means such as the Internet or dedicated lines. (2) Substrate Processing Step As one of the substrate processing steps in the manufacturing process of a semiconductor device (equipment) using the substrate processing apparatus 100, an example of a processing sequence for forming a predetermined film on the first surface 300 of a substrate 200 having a first surface 300 and a second surface 400 composed of different materials will be described using Figures 3 to 5. In the following description, the operation of each component constituting the substrate processing apparatus 100 is controlled by the controller 121. Different substances are exposed on the first surface 300 and the second surface 400, respectively. Specifically, the first surface 300 is composed of a conductive substance and is a film with high conductivity, that is, a conductive film. The first surface 300 is, for example, a molybdenum (Mo) film, a titanium nitride (TiN) film, etc. The second surface 400 is composed of a non-conductive substance and is a film with lower conductivity than the first surface. The second surface 400 is, for example, an oxide film such as a silicon oxide (SiO) film, a semiconductor film, etc. In this embodiment, a film 500 composed of a conductive substance is selectively formed on the first surface 300 of the wafer 200 having the first surface 300 and the second surface 400. When the term "wafer" is used in this specification, it is intended to refer to the wafer itself, and also to the wafer and the laminated body of the predetermined layer or film formed on its surface. When the term "wafer surface" is used in this specification, it is intended to refer to the surface of the wafer itself, and also to the surface of the predetermined layer formed on the wafer. When it is recorded in this specification that "a predetermined layer is formed on the wafer", it is intended to refer to the case where the predetermined layer is directly formed on the surface of the wafer itself, and also to the case where the predetermined layer is formed on the layer formed on the wafer. When the term "substrate" is used in this specification, it has the same meaning as when the term "wafer" is used. (Wafer Loading) When loading a plurality of wafers 200 onto the wafer boat 217 (wafer filling), as shown in FIG1 , the wafer boat 217, supporting the plurality of wafers 200, is lifted by the boat elevator 115 and loaded into the processing chamber 201 (wafer loading). In this state, the sealing cap 219 seals the lower opening of the manifold 209 via the O-ring 220b. (Pressure and Temperature Adjustment) The processing chamber 201, i.e., the space where the wafers 200 are located, is evacuated by the vacuum pump 246 to a desired pressure (vacuum level). The pressure within the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is controlled based on the measured pressure information (pressure adjustment). The vacuum pump 246 is continuously operated until at least the end of processing the wafers 200. Furthermore, the processing chamber 201 is heated by the heater 207 to a desired processing temperature. The power level of the heater 207 is controlled based on the temperature information detected by the temperature sensor 263 to achieve the desired temperature distribution within the processing chamber 201 (temperature adjustment). The heating of the processing chamber 201 by the heater 207 continues until at least the end of processing the wafers 200. (First Gas Supply, Step S11) First, a first gas containing a first element is supplied to the wafer 200 in the processing chamber 201. Specifically, valve 243a is opened to allow the first gas to flow into the gas supply pipe 232a. The first gas is flow-regulated by MFC 241a, supplied into the processing chamber 201 through nozzle 249a, and exhausted through exhaust pipe 231. Simultaneously, valve 243c is opened to allow an inert gas to flow into the gas supply pipe 232c. The inert gas is flow-regulated by MFC 241c, supplied into the processing chamber 201 along with the first gas, and exhausted through exhaust pipe 231. Furthermore, to prevent the first gas from entering nozzle 249b, valve 243d is opened to allow the inert gas to flow into the gas supply pipe 232d. The inert gas is supplied into the processing chamber 201 through gas supply pipe 232d and nozzle 249b and exhausted through exhaust pipe 231. At this time, the main gas flowing in the processing chamber 201 is the first gas containing the first element. The processing conditions of step S11 may include: temperature of the wafer 200: 300-700° C.; first gas supply time: 1-60 seconds; and partial pressure of the first gas: 10-10000 Pa. By supplying the first gas, a substance X containing the first element is formed on at least a portion of the surface of wafer 200. Here, substance X refers to molecules of the first gas or / and a portion of the molecular structure of the first gas that are chemically or physically adsorbed on the surface of wafer 200, and is at least one of a substance containing the first element, a compound containing the first element chemically bonded to another element, or a reduced monomer of the first element. Specifically, when a metal-containing gas is used as the first gas, substance X refers to molecules of the metal-containing gas or / and a portion of the molecular structure of the metal-containing gas, and is at least one of a substance containing the metal element, a compound containing the metal element chemically bonded to another element, or a reduced monomer of the metal element. More specifically, substance X can be, for example, a molecule of a Mo-containing gas, a portion of the molecular structure of a Mo-containing gas, or Mo. 4(A) to 4(D) are diagrams illustrating the conditions on the wafer 200 in this step. Here, in this aspect, the incubation time of the first gas on the second surface 400 is longer than the incubation time of the first gas on the first surface 300. Therefore, more substance X containing the first element is formed on the first surface 300 than on the second surface 400. Here, the incubation time refers to the time taken from the start of gas supply to a specific surface until gas molecules begin to adsorb or a film begins to form on the surface. That is, it takes longer for the molecules of the first gas to begin to adsorb on the second surface 400 than on the first surface 300. Therefore, as shown in FIG4(A), even if the first gas is supplied onto the wafer 200 having the first surface 300 and the second surface 400, it is more difficult for the substance X to form on the second surface 400 than on the first surface 300. However, even when the supply time of the first gas in this step is set to a time shorter than the incubation time of the first gas on the second surface 400, as shown in FIG4(B), the substance X containing the first element may form on a portion of the second surface 400, causing selective damage. Furthermore, each time the processing cycle is repeated, the substance X containing the first element increases, centering on the selective damage, and the substance X may also form on the second surface 400. Here, the first gas has a property of removing substance X. Thus, in this step, while forming substance X containing the first element, substance X containing the first element formed on wafer 200 as shown in FIG. 4(C) and FIG. 4(D) is removed. In this embodiment, the amount of substance X formed per unit time on the first surface 300 exceeds the amount of substance X removed per unit time. Furthermore, the amount of substance X formed per unit time on the second surface 400 is less than the amount of substance X removed per unit time. Consequently, in this step, as shown in FIG4(D), substance X is easily formed on the first surface 300, while it is difficult to form on the second surface 400. As described above, in this step, due to the difference in incubation time of the first gas between the first surface 300 and the second surface 400 and the removal of the substance X containing the first element, the substance X containing the first element is preferentially formed on the first surface 300 compared to the second surface 400 . In other words, the first gas forms a substance X containing the first element on the first surface 300 and has the effect of etching the substance X. That is, in the technology of the present invention, while the substance X is formed on the first surface 300 by the first gas, the substance X on the second surface 400 can also be etched simultaneously. Thus, for example, even if additional processing such as an etching step on the substance X fails to remove selective damage, the substance X containing the first element can still be selectively formed on the first surface 300. Furthermore, this step can be performed under conditions that allow the formation of a substance X containing the first element on at least a portion of the second surface 400. This facilitates the formation of selective damage on the second surface 400, and instead increases the amount of the substance X containing the first element formed on the first surface 300 per unit time. Furthermore, even in such a case, the selective damage on the second surface 400 is also removed by removing the substance X containing the first element in this step. Therefore, by performing this step under conditions that allow the formation of a substance X containing the first element on at least a portion of the second surface 400, the amount of the substance X formed on the first surface 300 per unit time can be increased, and good selectivity can be achieved. According to verification by the inventors of the present invention, in this step, it was confirmed that the substance X containing the first element formed on the second surface 400 (i.e., the non-conductive material) was preferentially removed. In other words, the etching rate of the non-conductive material by the first gas was lower than the etching rate of the conductive material. This allowed selective removal of the substance X on the second surface 400 without damaging the non-conductive material constituting the second surface 400. As the first gas, a gas containing a metal element as the first element and a halogen element can be used. As the metal element, for example, metal elements of Groups 3 to 14 of the 4th to 6th periods can be used. Preferably, transition metal elements of Groups 3 to 12 can be used as the metal element. In this case, the effect of this aspect can be further obtained. As the metal element, it is further preferred to use transition metal elements of the 5th period. In this case, the effect of this aspect can be further obtained. As the transition metal element of the 5th period, for example, Mo can be used. In this case, it is particularly easy to obtain the effect of this aspect. As the halogen element, for example, chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. As the halogen element, one or more of these can be used. Specifically, as the first gas, for example, a gas containing Mo and Cl can be used. In this case, the effect of this embodiment can be particularly easily obtained. As the gas containing Mo and Cl, for example, a gas containing molybdenum dioxide dichloride (MoO 2Cl 2) Gas, molybdenum oxide tetrachloride (MoOCl 4) Gas, molybdenum pentachloride (MoCl 5) Gas, molybdenum tetrachloride (MoCl 4) Any one of gases, etc., or a gas containing one or more of these gases. Furthermore, when a gas containing a transition metal element from the fifth period having an electron orbit similar to that of Mo and Cl is used as the first gas, the same effect as when a gas containing Mo and Cl is used can be easily obtained. Examples of transition metal elements from the fifth period that can be used include yttrium (Y), zirconium (Zr), niobium (Nb), titania (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and cadmium (Cd). As an inert gas, for example, nitrogen (N 2) In addition to the inert gas, argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas and the like can also be used. As the inert gas, one or more of these can be used. (Flushing, step S12) After a substance X containing the first element is formed on at least a portion of the wafer 200, while the valves 243a and 243b are closed, the valves 243c and 243d are opened, and an inert gas serving as a flushing gas is supplied to the gas supply pipes 232c and 232d through the gas supply pipes 232a and 232b, and the APC valve 244 of the exhaust pipe 231 is kept open, and the processing chamber 201 is vacuum-exhausted by the vacuum pump 246 to flush the processing chamber 201. (Supply of First Reactive Gas, Step S13) Next, the first reactive gas is supplied to the wafers 200 in the processing chamber 201. Specifically, valve 243b is opened to allow the first reactive gas to flow into the gas supply pipe 232b. The first reactive gas system has its flow rate regulated by MFC 241b, is supplied into the processing chamber 201 through nozzle 249b, and is exhausted through exhaust pipe 231. Simultaneously, valve 243d is opened to allow an inert gas to flow into the gas supply pipe 232d. The inert gas has its flow rate regulated by MFC 241d, is supplied into the processing chamber 201 along with the first reactive gas, and is exhausted through exhaust pipe 231. Furthermore, to prevent the first reactive gas from entering nozzle 249a, valve 243c is opened to allow the inert gas to flow into the gas supply pipe 232c. The inert gas is supplied into the processing chamber 201 through gas supply pipe 232c and nozzle 249a, and is exhausted through exhaust pipe 231. At this time, the main gas flowing in the processing chamber 201 is the first reaction gas. The processing conditions in step S13 may be exemplified as follows: Wafer 200 temperature: 300-700°C; First reaction gas supply time: 0.01-600 seconds; First reaction gas partial pressure: 4000-13000 Pa As the first reaction gas, for example, a gas that reacts with the substance X containing the first element and has reducing properties relative to the first gas can be used. As the first reaction gas, for example, hydrogen (H 2) Gas, deuterium (D 2) Borane (BH 3) Gas, diborane (B 2H 6) Gas, carbon monoxide (CO) gas, ammonia (NH 3) Gas, silane (SiH 4) Gas, disilane (Si 2H 6) Gas, trisilane (Si 3H 8) Gas, monogermane (GeH 4) Gas, digermane (Ge 2H 6) Gas, etc. Furthermore, as the first reaction gas, in addition to the reducing gas, a gas that reacts with the substance X to form a conductive substance, such as a nitride gas, a sulfide gas, a selenide gas, or a telluride gas, can be used. For example, when the first reaction gas is any one of a nitride gas, a sulfide gas, a selenide gas, and a telluride gas, a nitride film, a sulfide film, a selenide film, or a telluride film can be formed on the wafer. As the nitriding gas, for example, NH 3 gas, diazene (N 2H 2) Gas, hydrazine (N 2H 4) One or more nitride-based gases such as hydrogen sulfide gas. As the sulfide gas, for example, a gas containing hydrogen sulfide (H 2S), hydrogen disulfide (H 2S 2) Ammonium sulfide (NH 4) 2S), dimethyl sulfide ((CH 3) As the sulfiding gas, one or more of the above 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. (Flushing, step S14) After a layer containing the first element composed of substance X is formed on the wafer 200, an inert gas is supplied as a flushing gas according to the same processing procedure as the above-mentioned step S12. At the same time, while the APC valve 244 of the exhaust pipe 231 remains open, the vacuum pump 246 is used to vacuum exhaust the processing chamber 201 and flush the processing chamber 201. (Perform a Predetermined Number of Times, Step S15) The first cycle of non-simultaneously performing steps S11 to S14 is performed a first number of times (n times, where n is an integer greater than or equal to 1 or 2). The first cycle is performed, for example, 1 to 200 times. As shown in FIG5 , a film 500 containing the first element having a predetermined thickness is formed on the first surface 300 of the wafer 200, which is at least a portion of the wafer 200 and has the first surface 300 and the second surface 400. The film 500 containing the first element is a film made of a conductive material. Examples of the film made of a conductive material include a metal-containing film containing a metal element. Examples of the metal-containing film include a Mo-containing film. Here, when the first gas and the first reactive gas are supplied simultaneously, the reaction between the first gas and the first reactive gas in the gas phase triggers the formation of a substance X containing the first element on the wafer 200. In this case, the reaction between the first gas and the first reactive gas easily consumes the gas at locations on the wafer surface where the gas can easily reach. On the other hand, sufficient supply of the first gas and the first reactive gas is difficult to achieve at locations where the gas cannot reach. Consequently, the thickness of the film formed on the wafer surface tends to vary. In this aspect, by supplying the first gas and the first reactive gas asynchronously, a sufficient amount of the first gas can reach locations that are difficult for the first gas to reach before reacting with the first reactive gas. This improves the uniformity of the film thickness on the wafer surface. When using, for example, MoCl 5 gas as the first gas, and use, for example, H When 2 gases are used as the first reaction gas, MoCl 5Gas and H 2 gas reaction, whereby MoCl 5 Cl in the gas is replaced by H 2 gas reduction, forming a molybdenum (Mo) film as a metal-containing film on the first surface 300 of the wafer 200 as substance X. At this time, hydrogen chloride (HCl) and Cl 2. Reaction byproducts such as the second gas. By performing purge between the first gas supply and the first reaction gas supply, the gas or reaction byproducts remaining in the processing chamber 201 are removed. (Post-Purge and Atmospheric Pressure Restoration) Inert gas is supplied into the processing chamber 201 through the gas supply pipes 232c and 232d and exhausted through the exhaust pipe 231. The inert gas system serves as a purge gas. This purges the processing chamber 201, removing any remaining gases or reaction byproducts (post-purge). Subsequently, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure restoration). Wafer Unloading: The boat elevator 115 lowers the sealing cover 219, 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 (wafer unloading). The processed wafers are then removed from the boat 217 (wafer unloading). (3) Other Aspects Next, other aspects of the substrate processing steps and substrate processing apparatus in the above-mentioned aspects will be described in detail. In the following aspects, only the differences from the above-mentioned aspects will be described in detail. (Second Aspect) In this aspect, for example, a second gas supply system and a second reactive gas supply system are added to the aforementioned substrate processing apparatus 100. Specifically, a second gas supply pipe 232e, which supplies the second gas, is connected downstream of valve 243a of gas supply pipe 232a, that is, upstream of its connection with gas supply pipe 232c. Furthermore, a second reactive gas supply pipe 232f, which supplies the second reactive gas, is connected downstream of valve 243b of gas supply pipe 232b, that is, upstream of its connection with gas supply pipe 232d. Gas supply pipes 232e and 232f are provided, in order from the upstream side, with MFCs 241e and 241f, and valves 243e and 243f, respectively. The gas supply pipe 232e, MFC 241e, and valve 243e constitute the second gas supply system. The gas supply pipe 232f, the MFC 241f, and the valve 243f constitute a second reaction gas supply system. In this embodiment, as shown in FIG6 , after a first cycle of non-simultaneously performing steps S11 to S15 is performed n times, a second cycle of non-simultaneously performing steps S21 to S25 is performed m times. In other words, a second cycle is performed under conditions different from those of the first cycle. This allows the film containing the first element to be selectively formed on the first surface 300 of the wafer 200, thereby optimizing selectivity and film formation rate. (Supplying the Second Gas, Step S21) After performing Steps S11 to S15 above and forming a film containing the first element on at least a portion of the wafer 200, the second gas containing the first element is supplied to the wafer 200 in the processing chamber 201. Specifically, valve 243e is opened to allow the second gas to flow into the gas supply pipe 232e. The second gas is flow-regulated by MFC 241e, supplied into the processing chamber 201 through nozzle 249a, and exhausted from exhaust pipe 231. Simultaneously, valve 243c is opened to allow an inert gas to flow into the gas supply pipe 232c. The inert gas is flow-regulated by MFC 241c, supplied into the processing chamber 201 along with the second gas, and exhausted from exhaust pipe 231. Furthermore, to prevent the second gas from entering nozzle 249b, valve 243d is opened to allow the inert gas to flow into the gas supply pipe 232d. The inert gas is supplied into the processing chamber 201 through the gas supply pipe 232 d and the nozzle 249 b , and is exhausted from the exhaust pipe 231 . At this time, the main gas flowing in the processing chamber 201 is a second gas containing the first element. As the second gas, for example, a gas containing a metal element as the first element and a halogen element can be used. As the second gas, one or more of the gases exemplified as the first gas can be used. In this aspect, the "substance X containing the first element" used in the above aspect further includes "at least one or more of a substance containing the first element, a compound containing the first element chemically bonded to another element, or a reduced monomer of the first element, which is a molecule of the second gas chemically or physically adsorbed on the surface of wafer 200 or / and a part of the molecular structure of the second gas." In step S21, the second gas is supplied to form substance X containing the first element on at least a portion of wafer 200. Here, the incubation time of the second gas on the first surface 300 may be different from the incubation time on the second surface 400. For example, the incubation time of the second gas on the second surface 400 may be longer than that on the first surface 300. In this way, in the second cycle, a film can be selectively formed on the first surface 300 relative to the second surface 400, thereby improving selectivity. Furthermore, in step S21, at least a portion of the substance X formed on the wafer 200 may be removed. Furthermore, the ease of removing the substance X may be different between step S11 and step S21. The following description uses as an example a case where the substance X is removed more easily in step S21 than in step S11 (in other words, a case where the substance X is removed more easily in the second cycle than in the first cycle). In step S21, an example of a condition that makes the substance X formed on wafer 200 easier to remove than in step S11 is to use, as the second gas, a gas that is more reactive than the first gas with the substance X containing the first element formed on wafer 200. In other words, by using a gas different from the first gas as the second gas, the ease of removing the substance X containing the first element can be changed between the first cycle using the first gas and the second cycle using the second gas. As the second gas having a higher reactivity than the first gas to the substance X containing the first element, for example, a gas containing a larger number of halogen elements per molecule than the first gas can be used. 2Cl When 2 gas is used as the first gas, for example, MoCl 5 gas etc. as the second gas. In step S11, MoO 2Cl The processing conditions when using 2 gases as the first gas are as follows: Wafer 200 temperature: 300-700°C; First gas supply time: 1-60 seconds; First gas partial pressure: 10-10000 Pa; First number of times: 1-200 times In step S21, MoCl is used The processing conditions when using 5 gas as the second gas can be exemplified as follows: Wafer 200 temperature: 300-700°C; Second gas supply time: 1-60 seconds; Second gas partial pressure: 10-10000 Pa; Second number of times: 1-50 times In step S21, as an example of a condition that makes it easier to remove substance X formed on wafer 200 compared to step S11, the partial pressure of the second gas in processing chamber 201 (the space where wafer 200 is located) in step S21 can be set to be higher than the partial pressure of the first gas in processing chamber 201 in step S11. Thus, by varying the partial pressures in steps S11 and S21, the ease of removing substance X containing the first element in the first and second periods can be varied. Furthermore, in this case, even when using gases having the same molecular structure as the first and second gases, the ease of removing substance X containing the first element in the first and second periods can be varied. When removing the substance X containing the first element formed on the wafer 200, other conductive substances, such as the conductive substance constituting the first surface 300, may also be removed. As in this embodiment, by performing the first and second cycles with different removal facilitations for the substance containing the first element, damage to other conductive substances can be suppressed, and selectivity and film formation rate can be optimized. For example, the first cycle is performed first, followed by the second cycle. In this case, during the first cycle, substance X containing the first element is relatively difficult to remove, thereby suppressing damage to the conductive material constituting the first surface 300 (etching of the conductive material), and allowing substance X containing the first element to be formed on the first surface 300. Furthermore, during the second cycle, substance X containing the first element is already formed on the first surface 300, making it difficult to remove the conductive material constituting the first surface 300. In other words, damage to conductive materials other than substance X can be suppressed. Furthermore, in a gas containing the first element, the substance X containing the first element is easily removed, and thus a film can be formed selectively and well. However, there may be substances with low vapor pressure. For example, MoCl 5 Gas and MoO 2Cl 2 gases, although it is easy to form a film selectively and well, it is a gas with a low vapor pressure. When using this gas to process a wafer 200 with a large surface area, it is sometimes difficult to supply a sufficient amount of gas to the entire surface of the processed wafer 200. In this embodiment, a gas with a low vapor pressure that is easy to form a film selectively and well on the wafer 200, and a gas with a high vapor pressure that is difficult to form a film selectively and well are used respectively. Thereby, even when the surface area of ​​the wafer 200 is large, a film containing the first element can be selectively and well formed on the first surface 300. In addition, it is preferable to set the conditions of each step in the following embodiment: by processing the substrate as a whole, it is easy to form a film selectively and well on the wafer 200, and the consumption of the gas with a low vapor pressure is less than the consumption of the gas with a high vapor pressure that is difficult to form a film selectively and well. (Flushing, step S22) After a substance X containing the first element is formed on at least a portion of the wafer 200, an inert gas is supplied as a flushing gas by the same processing procedure as the above-mentioned step S12, and the APC valve 244 of the exhaust pipe 231 is kept open, and the inside of the processing chamber 201 is vacuum-exhausted by the vacuum pump 246 to flush the inside of the processing chamber 201. (Supply of Second Reactive Gas, Step S23) Furthermore, the second reactive gas is supplied to the wafers 200 in the processing chamber 201. Specifically, valve 243f is opened to allow the second reactive gas to flow into the gas supply pipe 232f. The second reactive gas is flow-regulated by MFC 241f, supplied into the processing chamber 201 through nozzle 249b, and exhausted through exhaust pipe 231. Simultaneously, valve 243d is opened to allow an inert gas to flow into the gas supply pipe 232d. The inert gas is flow-regulated by MFC 241d, supplied into the processing chamber 201 along with the second reactive gas, and exhausted through exhaust pipe 231. Furthermore, to prevent the second reactive gas from entering nozzle 249a, valve 243c is opened to allow the inert gas to flow into the gas supply pipe 232c. The inert gas is supplied into the processing chamber 201 through gas supply pipe 232c and nozzle 249a, and exhausted through exhaust pipe 231. At this time, the main gas flowing in the process chamber 201 is the second reaction gas. As the second reactant gas, for example, a gas that reacts with the substance X containing the first element, that is, a gas that has a reducing property with respect to the second gas, can be used. Furthermore, as the second reactant gas, for example, a gas that reacts with the substance X to form a conductive substance, such as a nitriding gas, a sulfiding gas, a seleniding gas, or a telluride gas, can be used. As the second reactant gas, one or more of the gases listed as examples for the first reactant gas can be used. (Flushing, step S24) After a layer containing the first element is formed on the wafer 200, an inert gas is supplied as a flushing gas by the same processing procedure as the above-mentioned step S12, and the APC valve 244 of the exhaust pipe 231 is kept open, and the processing chamber 201 is vacuum-exhausted by the vacuum pump 246 to flush the processing chamber 201. (Implement a predetermined number of times, step S25) By performing the second cycle of the above steps S21 to S24 non-simultaneously for a second number of times (m times, m is an integer greater than or equal to 1 or 2), a film containing the first element of a predetermined thickness is formed on at least a portion of the wafer 200, i.e., the first surface 300. Furthermore, in this embodiment, the same gas as the first gas described above can be used as the second gas. This modification also achieves the same effects as the above embodiment. In this modification, a gas supply system separate from the first gas supply system is not required as the second gas supply system, thereby simplifying the device configuration. Regarding the second aspect, the example of performing a first cycle including steps S11 to S15 n times and then performing a second cycle including steps S21 to S25, which is more likely to remove substance X than the first cycle, m times has been described. However, the present aspect is not limited to this. For example, the second cycle including steps S21 to S25, which is more likely to remove substance X than the first cycle, may be performed m times, and then the first cycle including steps S11 to S15 may be performed n times. In this case, substance X is easily removed during the first cycle, making it easier to remove selective damage on the second surface 400. Furthermore, in the second cycle, there is almost no selective damage on the second surface, so even when using a second gas with low etching properties, selective damage is less likely to occur. In contrast, substance X is less easily removed from the first surface. This improves selectivity and film formation rate. (Third Aspect) In this aspect, a processing cycle is performed multiple times. This processing cycle includes a first cycle in which steps S11 to S15 of the second aspect are performed a first number of times (n times, where n is an integer greater than or equal to 1 or 2), and a second cycle in which steps S21 to S25 are performed a second number of times (m times, where m is an integer greater than or equal to 1 or 2). Furthermore, the processing cycles performed after the Nth (N is an integer greater than or equal to 2) are performed under conditions that differ in the ease of removing the substance X containing the first element formed on the wafer 200 compared to the processing cycles performed before the N-1th (N-1) ... This allows combining treatment cycles before the N-1th cycle and treatment cycles after the Nth cycle, which differ in the ease with which the substance X containing the first element can be removed. This can suppress damage to other conductive substances and optimize selectivity and film formation rate. For example, the processing cycles performed after the Nth time may differ from those performed before the N-1th time by varying at least one of the first and second times. Furthermore, for example, the processing cycles performed after the Nth time may differ from those performed before the N-1th time by varying at least one of the supply time of the first gas in step S11 and the supply time of the second gas in step S21. Furthermore, for example, the processing cycles performed after the Nth time may differ from those performed before the N-1th time by varying at least one of the partial pressure of the first gas in the processing chamber 201 in step S11 and the partial pressure of the second gas in the processing chamber 201 in step S21. By performing at least one of these steps, the ease of removing the substance X containing the first element can be varied between processing cycles. For example, substance X containing the first element is more easily removed in the Nth and subsequent processing cycles than in the N-1th and subsequent processing cycles. In this case, since substance X containing the first element is relatively difficult to remove in the N-1th and subsequent processing cycles, damage to other conductive materials can be suppressed, and substance X containing the first element can be formed on first surface 300. Furthermore, in the Nth and subsequent processing cycles, since substance X containing the first element is already formed on first surface 300, the conductive material constituting first surface 300 is less likely to be removed. In other words, damage to conductive materials other than substance X can be suppressed, and a film containing the first element can be formed with good selectivity. Specifically, for example, in order to make it easier to remove substance X containing the first element in the processing cycle after the Nth time than in the processing cycle before the N-1th time, the supply time of the second gas after the Nth time is made longer than the supply time of the second gas before the N-1th time. Furthermore, in order to make it easier to remove substance X containing the first element in the processing cycles after the Nth time compared to the processing cycles before the N-1th time, the first number after the Nth time may be smaller than the first number before the N-1th time. Furthermore, the second number after the Nth time may be larger than the second number before the N-1th time. Furthermore, the supply time of the first gas after the Nth time may be shorter than the supply time of the first gas before the N-1th time. Furthermore, the partial pressure of the first gas after the Nth time may be smaller than the partial pressure of the first gas before the N-1th time. Furthermore, the partial pressure of the second gas after the Nth time may be larger than the partial pressure of the second gas before the N-1th time. Furthermore, the substance containing the first element may be removed more easily in the treatment cycles before the N-1th cycle than in the treatment cycles after the Nth cycle. That is, the substance X containing the first element may be removed more difficultly in the treatment cycles after the Nth cycle than in the treatment cycles before the N-1th cycle. To make the substance X containing the first element more difficult to remove in the treatment cycles after the Nth cycle than in the treatment cycles before the N-1th cycle, the first number after the Nth cycle may be greater than the first number before the N-1th cycle. Furthermore, the second number after the Nth cycle may be less than the second number before the N-1th cycle. Furthermore, the supply time of the first gas after the Nth cycle may be longer than the supply time of the first gas before the N-1th cycle. Furthermore, the supply time of the second gas after the Nth cycle may be shorter than the supply time of the second gas before the N-1th cycle. Furthermore, the partial pressure of the first gas after the Nth cycle may be greater than the partial pressure of the first gas before the N-1th cycle. Furthermore, the partial pressure of the second gas after the Nth time may be made smaller than the partial pressure of the second gas before the N-1th time. In this case, since substance X is easily removed in the N-1th processing cycle and before, selective damage on the second surface 400 is easily eliminated. Furthermore, since there is almost no selective damage on the second surface 400 in the Nth processing cycle and thereafter, even when a second gas with low etching properties is used, selective damage is less likely to occur. In contrast, substance X is less likely to be removed from the first surface 300. This improves selectivity and film formation rate. Furthermore, in the above-described aspects, an example of film formation using a batch-type substrate processing apparatus that processes multiple substrates at a time is described. The present invention is not limited to the above-described aspects and can also be appropriately applied to film formation using, for example, a single-wafer-type substrate processing apparatus that processes one or more substrates at a time. Furthermore, in the above-described aspects, an example of film formation using a substrate processing apparatus having a hot-wall processing furnace is described. The present invention is not limited to the above-described aspects and can also be appropriately applied to film formation using a substrate processing apparatus having a cold-wall processing furnace. The above-mentioned processing sequence can also be carried out continuously (in situ) in the same processing chamber (processing container). In addition, at least any one of the processing and any other processing in the above-mentioned processing sequence can be carried out in different processing chambers (processing containers) (non-in situ). In either case, the same effect as the above-mentioned state can be obtained. In addition, when these processes are carried out in situ, substrate contamination, changes in the surface state of the substrate, etc. that may be caused by moving the substrate out of the processing room or moving it in from the processing room can be suppressed. In addition, when these processes are carried out in situ, the transition time between processes can be shortened. On the other hand, when these processes are carried out non-in situ, each process can be carried out in parallel in different processing chambers, and productivity can be improved accordingly. Furthermore, when using these substrate processing apparatuses, each process can be performed according to the same processing procedures and processing conditions as those of the above-mentioned aspects and modifications, and the same effects as those of the above-mentioned aspects and modifications can be obtained. The above-mentioned aspects or modifications may be used in combination as appropriate. The processing procedures and processing conditions in this case may be, for example, the same as those in the above-mentioned aspects or modifications. While the aspects and modifications of the present invention have been specifically described above, the aspects and modifications of the present invention are not limited to the above-described aspects and modifications, and various modifications can be made without departing from the spirit of the present invention. 100: Substrate processing apparatus 115: Wafer boat elevator 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 220a, 220b: O-ring 231: Exhaust pipe 232a, 232b, 232c, 232d, 232e, 232f: Gas supply pipe 241a, 241b, 241c, 241d, 241e, 241f: Mass flow controller (MFC) 243a, 243b, 243c, 243d, 243e, 243f: Valve 244: APC valve 245: Pressure sensor 246: Vacuum pump 248: Concentrated supply system 249a, 249b: Nozzle 250a, 250b: Gas supply hole 255: Rotating shaft 263: Temperature sensor 267: Rotating mechanism 300: First surface 400: Second surface 500: Membrane FIG1 is a schematic longitudinal cross-sectional view of a vertical processing furnace of a substrate processing apparatus according to one embodiment of the present invention. FIG2 is a schematic structural diagram of a controller of a substrate processing apparatus according to one embodiment of the present invention, which is a block diagram showing the control system of the controller. FIG3 is a diagram showing a substrate processing step according to one embodiment of the present invention. FIG4(A) is a diagram showing a situation when a first gas is supplied to a substrate having a first surface and a second surface; FIG4(B) is a diagram showing a situation when a substance containing a first element is formed on the first surface and the second surface; FIG4(C) is a diagram showing a situation when the first gas is supplied to the substrate of FIG4(B) and the first gas removes the substance containing the first element formed on the substrate; FIG4(D) is a diagram showing a situation on the substrate after at least a portion of the substance containing the first element is removed. FIG5 is a schematic diagram for explaining a film formed on a substrate by a substrate processing step according to one embodiment of the present invention. FIG6 is a diagram showing a substrate processing step in a second embodiment of the present invention.

Claims

1. A substrate processing method comprising the steps of performing a first cycle a first number of times and performing a second cycle a second number of times, thereby forming a film containing a first element on at least a portion of the substrate, wherein the first cycle is performed non-simultaneously: (a1) supplying a first gas containing the first element to a substrate having a first surface and a second surface respectively composed of different substances, and forming a substance X containing the first element on at least a portion of the substrate, and (a2) supplying a first reactive gas that reacts with the substance X to the substrate; wherein the second cycle is performed as follows: (b1) supplying a second gas containing the first element to the substrate, and forming the substance X on at least a portion of the substrate, and (b2) supplying a second reactive gas that reacts with the substance X to the substrate; wherein the incubation time of the first gas on the second surface is longer than the incubation time on the first surface; and in (a1), removing a portion of the substance X formed on the substrate. In (a1), the amount of substance X formed on the first surface per unit time is set to exceed the amount of substance X removed from the first surface per unit time by the first gas, and in (a1), the amount of substance X formed on the second surface per unit time is set to be less than the amount of substance X removed from the second surface per unit time by the first gas; in (b1), a portion of the substance X formed on the substrate is removed, and (b1) is performed under the condition that the substance X formed on the substrate is easier to remove than in (a1).

2. The substrate processing method as described in claim 1, wherein, (a1) is carried out under conditions in which the substance X can be formed on at least a portion of the second surface.

3. The substrate processing method as described in claim 1, wherein, The first surface is made of a conductive material, the second surface is made of a non-conductive material, and the film is made of a conductive material.

4. The substrate processing method as described in claim 3, wherein, In (a1), the substance X formed on the second surface is preferentially removed compared to the non-conductive substance.

5. The substrate processing method as described in claim 1, wherein, The incubation time of the second gas on the second surface is longer than that on the first surface.

6. The substrate processing method as described in claim 1, wherein, The partial pressure of the second gas in the space where the substrate exists in (b1) is greater than the partial pressure of the first gas in the space where the substrate exists in (a1).

7. The substrate processing method as described in claim 1, wherein, The second gas is more reactive to the substance X formed on the substrate than the first gas.

8. The substrate processing method as described in claim 1, wherein, The processing cycle, which includes the first cycle performed the first time and the second cycle performed the second time, is performed a plurality of times. The processing cycle performed after the Nth time is performed under conditions where the ease of removing the substance X formed on the substrate is different compared to the processing cycle performed before the N-1th time, and N is an integer of 2 or more.

9. The substrate processing method as described in claim 8, wherein, The processing cycle performed after the Nth time is different from the processing cycle performed before the N-1th time in that at least one of the first number and the second number is different.

10. The substrate processing method as described in claim 8, wherein, The processing cycle performed after the Nth time is different from the processing cycle performed before the N-1th time in terms of at least one of the supply time of the first gas in (a1) and the supply time of the second gas in (b1).

11. The substrate processing method as described in claim 8, wherein, The processing cycle performed after the Nth time is different from the processing cycle performed before the N-1th time in terms of at least one of the partial pressure of the first gas in the space where the substrate exists in (a1) and the partial pressure of the second gas in the space where the substrate exists in (b1).

12. The substrate processing method according to any one of claims 1 to 11, wherein, The first gas mentioned above contains a metallic element as the first element mentioned above, as well as a halogen element.

13. The substrate processing method as described in claim 12, wherein, The aforementioned metal elements are transition metals from the fifth period.

14. The substrate processing method as described in claim 12, wherein, The halogen element mentioned above is chlorine.

15. The substrate processing method as described in claim 12, wherein, The first gas mentioned above is any one of MoO2Cl2 gas, MoOCl4 gas, MoCl5 gas, and MoCl4 gas.

16. A method for manufacturing a semiconductor device, comprising the steps of performing a first cycle a first number of times and performing a second cycle a second number of times, thereby forming a film containing a first element on at least a portion of a substrate, wherein the first cycle is performed non-simultaneously: (a1) supplying a first gas containing the first element to a substrate having a first surface and a second surface respectively made of different materials, and forming a substance X containing the first element on at least a portion of the substrate, and (a2) supplying a first reactive gas that reacts with the substance X to the substrate; wherein the second cycle is performed as follows: (b1) supplying a second gas containing the first element to the substrate, and forming the substance X on at least a portion of the substrate, and (b2) supplying a second reactive gas that reacts with the substance X to the substrate; wherein the culture time of the first gas on the second surface is longer than the culture time on the first surface; and in (a1), removing a portion of the substance X formed on the substrate. In (a1), the amount of substance X formed on the first surface per unit time is set to exceed the amount of substance X removed from the first surface per unit time by the first gas, and in (a1), the amount of substance X formed on the second surface per unit time is set to be less than the amount of substance X removed from the second surface per unit time by the first gas; in (b1), a portion of the substance X formed on the substrate is removed, and (b1) is performed under the condition that the substance X formed on the substrate is easier to remove than in (a1).

17. A substrate processing apparatus comprising: a first gas supply system for supplying a first gas containing a first element to a substrate having a first surface and a second surface respectively made of different materials; a first reactant gas supply system for supplying the substrate with a first reactant gas that reacts with a substance X containing the first element; and a control unit configured to control the first gas supply system and the first reactant gas supply system to perform processing for a first number of times in a first cycle and processing for a second number of times in a second cycle, thereby forming a film containing the first element on at least a portion of the substrate, wherein the first cycle is performed non-simultaneously as follows: (a1) supplying the first gas to the substrate and forming the substance X on at least a portion of the substrate, and (a2) supplying the first reactant gas to the substrate; wherein the second cycle is performed as follows: (b1) A process of supplying a second gas containing the first element to the substrate, and forming the substance X on at least a portion of the substrate, and (b2) A process of supplying a second reactive gas that reacts with the substance X to the substrate; The incubation time of the first gas on the second surface is longer than the incubation time on the first surface; and in (a1), at least a portion of the substance X formed on the substrate is removed; in (a1), the amount of the substance X formed on the first surface per unit time is set to exceed the amount of the substance X removed from the first surface per unit time by the first gas, and in (a1), the amount of the substance X formed on the second surface per unit time is set to be less than the amount of the substance X removed from the second surface per unit time by the first gas; in (b1), a portion of the substance X formed on the substrate is removed, and (b1) is performed under conditions where it is easier to remove the substance X formed on the substrate compared to (a1).

18. A program for executing a predetermined program by means of a computer on a substrate processing apparatus, the program being a program that performs a first cycle a first number of times and a second cycle a second number of times, and forming a film containing a first element on at least a portion of a substrate, wherein the first cycle is performed non-simultaneously: (a1) a program that supplies a first gas containing the first element to a substrate having a first surface and a second surface respectively composed of different substances, and forms a substance X containing the first element on at least a portion of the substrate, and (a2) a program that supplies a first reactive gas to the substrate to react with the substance X; wherein the second cycle is performed as follows: (b1) a program that supplies a second gas containing the first element to the substrate, and forms the substance X on at least a portion of the substrate, and (b2) a program that supplies a second reactive gas to the substrate to react with the substance X; wherein the incubation time of the first gas on the second surface is longer than the incubation time on the first surface; and in (a1), at least a portion of the substance X formed on the substrate is removed. In (a1), the amount of substance X formed on the first surface per unit time is set to exceed the amount of substance X removed from the first surface per unit time by the first gas, and in (a1), the amount of substance X formed on the second surface per unit time is set to be less than the amount of substance X removed from the second surface per unit time by the first gas; in (b1), a portion of the substance X formed on the substrate is removed, and (b1) is performed under the condition that the substance X formed on the substrate is easier to remove than in (a1).

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