SUBSTRATE PROCESSING METHOD, SEMICONDUCTOR DEVICE MANUFACTURING APPARATUS, PROGRAM, AND SUBSTRATE PROCESSING APPARATUS

Abstract

To provide technology capable of forming a film with a desired thickness distribution in recesses of a substrate.SOLUTION: A method comprises the steps of (a) supplying first gas containing predetermined elements and a halogen element to a substrate in a processing chamber, (b) removing the first gas from the processing chamber, (c) forming a first layer containing the predetermined elements and having a halogen-terminated surface on the substrate by performing a cycle including (a) and (b) for a first predetermined number of times, (d) forming a second layer containing the predetermined elements on the substrate by supplying second gas containing the predetermined elements to the substrate on which the first layer is formed, and (e) forming a film containing the predetermined elements on the substrate by performing the cycle including (c) and (d) a second predetermined number of times.SELECTED DRAWING: Figure 4

Description

[Technical field]

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

[0002] 2. Description of the Related Art As one step in the manufacturing process of a semiconductor device, a film formation process is sometimes performed in which a film is formed by repeatedly performing a film formation step and an etching step (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2019-160962 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, in the conventional processes, for example, it may be difficult to form a film having a desired thickness distribution in a recess formed in a substrate having a recess formed on its surface.

[0005] An object of the present disclosure is to provide, for example, a technique capable of forming a film having a desired thickness distribution in a recessed portion of a substrate. [Means for solving the problem]

[0006] According to one aspect of the present disclosure, (a) supplying a first gas containing a predetermined element and a halogen element to a substrate in a processing chamber; (b) removing the first gas from the process chamber; (c) performing a cycle including steps (a) and (b) a first predetermined number of times to form a first layer on the substrate, the first layer containing the predetermined element and having a halogen-terminated surface; (d) supplying a second gas containing the predetermined element to the substrate on which the first layer is formed, thereby forming a second layer containing the predetermined element on the substrate; (e) performing a cycle including (c) and (d) a second predetermined number of times to form a film containing the predetermined element on the substrate; Techniques for doing so are provided. Effect of the Invention

[0007] According to the present disclosure, for example, it is possible to provide a technique that makes it possible to form a film having a desired thickness distribution in a recessed portion of a substrate. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, showing a processing furnace 202 portion in vertical cross section. [Diagram 2] FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and shows a processing furnace 202 portion in a cross-sectional view taken along line AA in FIG. [Diagram 3] FIG. 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a block diagram showing a control system of the controller 121. [Figure 4] FIG. 4 is a diagram showing a processing sequence according to an embodiment of the present disclosure. [Diagram 5] Fig. 5(a) is a partial enlarged cross-sectional view of the surface of wafer 200 in which recess 300 is provided. Fig. 5(b) is a partial enlarged cross-sectional view of the surface of wafer 200 after a first layer is formed in recess 300. Fig. 5(c) is a partial enlarged cross-sectional view of the surface of wafer 200 after a second layer is formed in recess 300. Fig. 5(d) is a partial enlarged cross-sectional view of the surface of wafer 200 after recess 300 is entirely filled with film 308. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] <One aspect of the present disclosure> Hereinafter, one embodiment of the present disclosure will be described mainly with reference to Figures 1 to 4 and 5(a) to 5(d). Note that the drawings used in the following description are all schematic, and the dimensional relationships of the elements, the ratios of the elements, etc. shown in the drawings do not necessarily match the actual ones. Furthermore, the dimensional relationships of the elements, the ratios of the elements, etc. between multiple drawings do not necessarily match.

[0010] (1) Configuration of the substrate processing device 1, the process furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is installed vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas by heat.

[0011] A reaction tube 203 is disposed concentrically with the heater 207 inside the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and is formed in a cylindrical shape with a closed upper end and an open lower end. A manifold 209 is disposed concentrically with the reaction tube 203 below the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS) and is formed in a cylindrical shape with an open upper end and a closed lower end. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a seal member. The reaction tube 203 is installed vertically like the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in a cylindrical hollow portion of the processing vessel. The processing chamber 201 is configured to be capable of accommodating a wafer 200 as a substrate. In the processing chamber 201, processing of the wafer 200 is performed.

[0012] In the processing chamber 201, nozzles 249a and 249b as a first supply unit and a second supply unit are provided so as to penetrate a side wall of the manifold 209, respectively. The nozzles 249a and 249b are also referred to as a first nozzle and a second nozzle, respectively. The nozzles 249a and 249b are made of a heat-resistant material such as quartz or SiC. Gas supply pipes 232a and 232b are connected to the nozzles 249a and 249b, respectively. The nozzles 249a and 249b are different nozzles and provided adjacent to each other.

[0013] Gas supply pipes 232a and 232b are provided with mass flow controllers (MFCs) 241a and 241b, which are flow rate controllers (flow rate control parts), and valves 243a and 243b, which are on-off valves, in order from the upstream side of the gas flow. Gas supply pipes 232c and 232d are connected to the gas supply pipe 232a downstream of the valve 243a. Gas supply pipe 232e is connected to the gas supply pipe 232b downstream of the valve 243b. Gas supply pipes 232c to 232e are provided with MFCs 241c to 241e and valves 243c to 243e in order from the upstream side of the gas flow. Gas supply pipes 232a to 232e are made of a metal material, such as SUS.

[0014] 2, the nozzles 249a and 249b are provided in a circular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, from the lower part to the upper part of the inner wall of the reaction tube 203, so as to rise upward in the arrangement direction of the wafers 200. That is, the nozzles 249a and 249b are provided in a region horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region where the wafers 200 are arranged, so as to extend along the wafer arrangement region. The gas supply holes 250a and 250b are each open toward the center of the wafer 200 in a plan view, and can supply gas toward the wafer 200. A plurality of gas supply holes 250a and 250b are provided from the lower part to the upper part of the reaction tube 203.

[0015] A first gas containing a predetermined element and a halogen element is supplied from the gas supply pipe 232a into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.

[0016] A second gas containing the same predetermined element as the first gas is supplied from the gas supply pipe 232b into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.

[0017] An etching gas is supplied from the gas supply pipe 232c into the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c.

[0018] From the gas supply pipes 232d and 232e, an inert gas is supplied into the processing chamber 201 via the MFCs 241d and 241e, the valves 243d and 243e, the gas supply pipes 232a and 232b, and the nozzles 249a and 249b. The inert gas acts as a purge gas, a carrier gas, a dilution gas, etc.

[0019] A first gas supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. A second gas supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. An etching gas supply system is mainly composed of the gas supply pipe 232c, the MFC 241c, and the valve 243c. An inert gas supply system is mainly composed of the gas supply pipes 232d and 232e, the MFCs 241d and 241e, and the valves 243d and 243e.

[0020] Since the second gas acts as a source gas (film formation gas), the second gas supply system is also called a source gas (film formation gas) supply system, and since the first gas acts as a film formation inhibiting gas, the first gas supply system is also called a film formation inhibiting gas supply system.

[0021] Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which the valves 243a to 243e and the MFCs 241a to 241e are integrated. The integrated supply system 248 is connected to the gas supply pipes 232a to 232e, and the supply operation of various substances (various gases) into the gas supply pipes 232a to 232e, that is, the opening and closing operation of the valves 243a to 243e and the flow rate adjustment operation by the MFCs 241a to 241e, are controlled by a controller 121 described later. The integrated supply system 248 is configured as an integrated or separate integrated unit, and can be attached and detached to and from the gas supply pipes 232a to 232e, etc., and maintenance, replacement, expansion, etc. of the integrated supply system 248 can be performed on an integrated unit basis.

[0022] An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided at the lower side of the side wall of the reaction tube 203. The exhaust port 231a may be provided along the side wall of the reaction tube 203 from the lower part to the upper part, i.e., along the wafer arrangement region. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit). The APC valve 244 is configured to be able to evacuate and stop the evacuation of the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is in operation, and further, to be able to adjust the pressure in the processing chamber 201 by adjusting the valve opening based on the pressure information detected by the pressure sensor 245 while the vacuum pump 246 is in operation. An exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. A vacuum pump 246 may be included in the exhaust system.

[0023] Below the manifold 209, a seal cap 219 is provided as a furnace port cover body capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal material such as SUS, and is formed in a disk shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a seal member that abuts against the lower end of the manifold 209. Below the seal cap 219, a rotation mechanism 267 is provided for rotating the boat 217, which will be described later. A rotation shaft 255 of the rotation mechanism 267 is made of a metal material such as SUS, and is connected to the boat 217 through the seal cap 219. The rotation mechanism 267 is configured to rotate the wafers 200 by rotating the boat 217. The seal cap 219 is configured to be vertically raised and lowered by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transfer device (transfer mechanism) that lifts and lowers the seal cap 219 to load and unload (transport) the wafer 200 into and out of the processing chamber 201. The transfer device functions as a providing device that provides the wafer 200 into the processing chamber 201.

[0024] A shutter 219s is provided below the manifold 209 as a furnace port cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is carried out of the processing chamber 201. The shutter 219s is made of a metal material such as SUS and is formed in a disk shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a seal member that comes into contact with the lower end of the manifold 209. The opening and closing operation (lifting and lowering operation, rotating operation, etc.) of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

[0025] The boat 217 as a substrate support is configured to support a plurality of wafers 200, for example 25 to 200, in multiple stages in a horizontal position and aligned vertically with their centers aligned, that is, arranged at intervals in a direction perpendicular to the surfaces of the wafers 200. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages.

[0026] A temperature sensor 263 serving as a temperature detector is installed in the reaction tube 203. By adjusting the power supply to the heater 207 based on temperature information detected by the temperature sensor 263, the temperature distribution in the process chamber 201 becomes a desired one. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0027] As shown in Fig. 3, the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122 configured as, for example, a touch panel, is connected to the controller 121. An external storage device 123 can also be connected to the controller 121.

[0028] The storage device 121c is composed of, for example, a flash memory, a hard disk drive (HDD), a solid state drive (SSD), etc. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe in which procedures and conditions of the substrate processing described later are described, etc. are recorded and stored in a readable manner. The process recipe is a combination of procedures in the substrate processing described later that are executed by the controller 121 in the substrate processing apparatus to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are collectively referred to simply as a program. In addition, the process recipe is also simply referred to as a recipe. In this specification, when the word program is used, it may include only a recipe, only a control program, or both. The RAM 121b is configured as a memory area (work area) in which the programs and data read by the CPU 121a are temporarily stored.

[0029] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241e, valves 243a to 243e, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, shutter opening / closing mechanism 115s, and the like.

[0030] The CPU 121a is configured to be able to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to an input of an operation command from the input / output device 122, etc. The CPU 121a is configured to be able to control the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241e, the opening and closing operations of the valves 243a to 243e, the opening and closing operation of the APC valve 244 and the pressure adjustment operation by the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, etc., in accordance with the contents of the read recipe.

[0031] The controller 121 can be configured by installing the above-mentioned program recorded and stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, and a semiconductor memory such as a USB memory or an SSD. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media. When the term recording media is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both of them. The program may be provided to the computer using a communication means such as the Internet or a dedicated line without using the external storage device 123.

[0032] (2) Substrate processing An example of a processing sequence for forming a film on a wafer 200 as a substrate as one step in a manufacturing process of a semiconductor device using the above-mentioned substrate processing apparatus will be described mainly with reference to FIG. 4 and FIG. 5(a) to FIG. 5(d). In this embodiment, as an example, a case where a recess 300 is formed on the surface of the wafer 200 will be described. In this specification, the term "recess" includes not only trenches and holes, but also structures in general that have a large internal surface area relative to the opening, such as lateral holes and through holes. In the following description, the operation of each part constituting the substrate processing apparatus 100 is controlled by a controller 121.

[0033] In the processing sequence of this embodiment, A step A of supplying a first gas containing a predetermined element and a halogen element to the wafer 200 in the processing chamber 201; Step B of removing the first gas from the processing chamber 201; a step C of forming a first layer 304 containing a predetermined element and having a halogen-terminated surface on the wafer 200 by performing a cycle including the steps A and B a first predetermined number of times (n times, where n is an integer of 1 or more); Step D of supplying a second gas containing a predetermined element to the wafer 200 on which the first layer 304 is formed, thereby forming a second layer 306 containing a predetermined element on the wafer 200; Step E of forming a film 308 containing a predetermined element on the wafer 200 by performing a cycle including steps C and D a second predetermined number of times (m times, where m is an integer equal to or greater than 1); Note that A to E in FIG. 4 indicate steps A to E, respectively.

[0034] In the following, an example in which a silicon (Si) film is formed as the film 308 will be described.

[0035] In this specification, the above-mentioned processing sequence may be expressed as follows for convenience: Similar notations will be used in the following explanations of modified examples and other aspects.

[0036] [(1st gas → purge) × n → 2nd gas] × m

[0037] 4 and the process sequence shown below, a purging step may be further performed after the step of supplying the second gas, in which case the process sequence will be described as an example in this embodiment.

[0038] [(1st gas → purge) × n → 2nd gas → purge] × m

[0039] The term "wafer" used in this specification may mean the wafer itself or a laminate of the wafer and a predetermined layer or film formed on its surface. The term "surface of a wafer" used in this specification may mean the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. When it is stated in this specification that "a predetermined layer is formed on a wafer", it may mean that a predetermined layer is formed directly on the surface of the wafer itself or that a predetermined layer is formed on a layer or the like formed on the wafer. When the term "substrate" is used in this specification, it is synonymous with the term "wafer".

[0040] (Wafer charge and boat load) When a plurality of wafers 200 are loaded into the boat 217 (wafer charge), the shutter 219s is moved by the shutter opening / closing mechanism 115s to open the lower end opening of the manifold 209 (shutter open). Thereafter, as shown in Fig. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat load). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.

[0041] As the wafer 200, for example, a single crystal silicon (Si) wafer can be used. In addition, a recess 300 is provided on the surface of the wafer 200, as shown in Fig. 5(a) to Fig. 5(d). The material of the surface (outermost surface) of the recess 300, that is, the surface of the inner wall of the recess 300, is not particularly limited, and examples thereof include single crystal Si (single crystal Si wafer itself), silicon film (Si film), germanium film (Ge film), silicon germanium film (SiGe film), silicon carbide film (SiC film), silicon nitride film (SiN film), silicon carbonitride film (SiCN film), silicon oxide film (SiO film), silicon oxynitride film (SiON), silicon oxycarbide film (SiOC film), silicon oxycarbonitride film (SiOCN film), silicon boronitride film (SiBN film), silicon boron carbonitride film (SiBCN film), boronitride film (BN film), and the like, and may be at least one of these.

[0042] (Pressure and temperature regulation) After the boat loading is completed, the inside of the processing chamber 201, i.e., the space in which the wafers 200 are present, is evacuated (reduced pressure exhaust) by the vacuum pump 246 so that the inside of the processing chamber 201 is at a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. Also, the wafers 200 in the processing chamber 201 are heated by the heater 207 so that the temperature is a desired processing temperature. At this time, the power supply to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. Also, the rotation mechanism 267 starts rotating the wafers 200. The evacuation inside the processing chamber 201 and the heating and rotation of the wafers 200 are all continued at least until the processing of the wafers 200 is completed.

[0043] Thereafter, steps A to E are performed in this order to perform a film formation process on the wafer 200. In this specification, the film formation process in the recesses 300 provided on the surface of the wafer 200 is also referred to as a filling process. Each of these steps will be described below.

[0044] [Step A] In step A, a first gas is supplied to the wafer 200 in the processing chamber 201 .

[0045] Specifically, the valve 243a is opened to allow the first gas to flow into the gas supply pipe 232a. The flow rate of the first gas is adjusted by the MFC 241a, and the first gas is supplied into the processing chamber 201 through the nozzle 249a and exhausted from the exhaust port 231a. At this time, the first gas is supplied to the wafer 200 (first gas supply). At this time, the valves 243d and 243e may be opened to supply an inert gas into the processing chamber 201 through each of the nozzles 249a and 249b.

[0046] The processing conditions in this step are as follows: Treatment temperature: 300 to 600°C, preferably 400 to 500°C Treatment pressure: 1k to 100kPa, preferably 20k to 50kPa First gas supply flow rate: 0.1 to 1 slm, preferably 0.2 to 0.5 slm First gas supply time: 1 to 10 minutes, preferably 3 to 6 minutes Inert gas supply flow rate (per gas supply pipe): 0 to 0.5 slm Examples are given below.

[0047] In this specification, the expression of a numerical range such as "300 to 600°C" means that the lower limit and the upper limit are included in the range. Therefore, for example, "300 to 600°C" means "300°C or more and 600°C or less". The same applies to other numerical ranges. In this specification, the process temperature means the temperature of the wafer 200 or the temperature in the process chamber 201, and the process pressure means the pressure in the process chamber 201. In addition, when the supply flow rate includes 0 slm, 0 slm means that the gas is not supplied. These are the same in the following explanations.

[0048] Under the above-mentioned conditions, a chlorosilane-based gas containing, for example, Si as a predetermined element and chlorine (Cl) as a halogen element and having Si-Cl bonds is supplied to the wafer 200 as the first gas, so that some of the Si-Cl bonds contained in the molecules of the gas react with the surface of the wafer 200, and the gas can be adsorbed onto the surface of the wafer 200. Also, under the above-mentioned conditions, the remaining Si-Cl bonds contained in the molecules of the first gas adsorbed onto the surface of the wafer 200 that have not reacted with the surface of the wafer 200 can be retained as they are, and a Cl termination (Si-Cl termination) that is a halogen termination can be formed on the surface of the wafer 200. Note that the adsorption of the first gas onto the surface of the wafer 200 may include a case where Si having dangling bonds reacts with the surface to cause chemical adsorption, as well as a case where the first gas that has Si-Cl bonds is physically adsorbed onto the surface.

[0049] After the first gas is adsorbed onto the surface of the wafer 200, the valve 243a is closed to stop the supply of the first gas into the processing chamber 201.

[0050] The first gas may be, for example, a halosilane-based gas containing a halogen element and Si as a predetermined element. The halogen element may be, for example, Cl, fluorine (F), bromine (Br), iodine (I), etc. The halosilane-based gas may be, for example, the above-mentioned chlorosilane-based gas containing Si and Cl.

[0051] As the first gas, for example, a chlorosilane-based gas such as dichlorosilane (SiH2Cl2, abbreviated as DCS) gas, tetrachlorosilane (SiCl4, abbreviated as STC) gas, hexachlorodisilane gas (Si2Cl6, abbreviated as HCDS) gas, octachlorotrisilane (Si3Cl8, abbreviated as OCTS) gas, etc. As the first gas, one or more of these can be used.

[0052] As the first gas, in addition to chlorosilane-based gases, fluorosilane-based gases such as tetrafluorosilane (SiF4) gas, difluorosilane (SiH2F2) gas, hexafluorodisilane (Si2F6, abbreviated as HFDS) gas, and octafluorotrisilane (Si3F8) gas, bromosilane-based gases such as tetrabromosilane (SiBr4) gas, bromosilane-based gases such as hexabromodisilane (Si2Br6, abbreviated as HBDS) gas and octabromotrisilane (Si3Br8) gas, and iodosilane-based gases such as tetraiodosilane (SiI4, abbreviated as STI) gas, diiodosilane (SiH2I2) gas, hexaiododisilane (Si2I6, abbreviated as HIDS) gas, and octaiodotrisilane (Si3I8) gas can be used. As the first gas, one or more of these can be used.

[0053] As the inert gas, for example, nitrogen (N2) gas, argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas, or other rare gases can be used. As the inert gas, one or more of these can be used. This also applies to each step described later.

[0054] [Step B] In step B, the inside of the processing chamber 201 is evacuated to remove gaseous substances remaining in the processing chamber 201 from the inside of the processing chamber 201. At this time, an inert gas is supplied into the processing chamber 201.

[0055] Specifically, the valves 243d and 243e are opened to allow the inert gas to flow into the gas supply pipes 232a and 232b. The inert gas is adjusted in flow rate by the MFCs 241d and 241e, supplied into the processing chamber 201 via the nozzles 249a and 249b, and exhausted from the exhaust port 231a. The inert gas supplied from the nozzles 249a and 249b acts as a purge gas, thereby purging the processing chamber 201 (purging).

[0056] The processing conditions in this step are as follows: Processing pressure: 10~100Pa Inert gas supply flow rate (per gas supply pipe): 0.1 to 1 slm Inert gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds The other processing conditions are the same as those in step A.

[0057] [Step C (Perform the cycle a specified number of times)] By performing a cycle of the above-mentioned steps A and B non-simultaneously, i.e., without synchronization, a first predetermined number of times (n times, n being an integer equal to or greater than 1), a layer containing a predetermined element (Si) and having a halogen-terminated (Cl-terminated) surface is formed as a first layer 304 on the outermost surface of the wafer 200 as a base.

[0058] In this step, for example, the density of the first layer 304 in a part of the inner surface of the recess 300 can be made higher than the density of the first layer 304 in the other part of the inner surface of the recess 300. Specifically, for example, by reducing the supply flow rate of the first gas per cycle or shortening the supply time of the first gas, the first gas is prevented from reaching the vicinity of the bottom of the inner surface of the recess 300, and the supply of the first gas is limited to the vicinity of the opening of the inner surface of the recess 300. By doing so, for example, it becomes easy to make the density of the first layer 304 in the vicinity of the opening higher than the density of the first layer 304 in the vicinity of the bottom (see FIG. 5(b)). At this time, by performing the first predetermined number of times two or more times, that is, the above-mentioned cycle two or more times, the density of the first layer 304 can be adjusted more easily. In this specification, the “layer density” on the inner surface of recess 300 can be considered to be synonymous with, for example, the number of adsorbed Si, etc. to which Cl, etc. are bonded (i.e., terminated with Cl, etc.) per unit area on the inner surface of recess 300, or the average thickness of the layer per unit area on the inner surface of recess 300.

[0059] Furthermore, in this step, by adjusting the execution time of step A per cycle (the supply time of the first gas) and the supply flow rate of the first gas, it is possible to set the ratio of the density of the first layer 304 formed near the bottom to the density of the first layer 304 formed near the opening of the inner surface of the recess 300 to a desired value. Specifically, for example, by adjusting the execution time of step A per cycle in a direction to shorten it from a predetermined time, or by adjusting the supply flow rate of the first gas in step A in a direction to decrease it from a predetermined flow rate, it is possible to control so as to reduce the ratio of the density of the first layer 304 formed near the bottom to the density of the first layer 304 formed near the opening of the inner surface of the recess 300.

[0060] [Step D] In step D, a second gas is supplied to the wafer 200 in the processing chamber 201 .

[0061] Specifically, the valve 243b is opened to allow the second gas to flow into the gas supply pipe 232b. The flow rate of the first gas is adjusted by the MFC 241b, and the first gas is supplied into the processing chamber 201 through the nozzle 249b and exhausted from the exhaust port 231a. At this time, the second gas is supplied to the wafer 200 (second gas supply). At this time, the valves 243d and 243e may be opened to supply an inert gas into the processing chamber 201 through each of the nozzles 249a and 249b.

[0062] The processing conditions in this step are as follows: Treatment temperature: 400 to 600°C, preferably 450 to 550°C Treatment pressure: 10 to 500 Pa, preferably 50 to 100 Pa Second gas supply flow rate: 1 to 5 slm, preferably 2 to 4 slm Second gas supply time: 10 to 120 minutes, preferably 30 to 90 minutes The other processing conditions are the same as those in step A.

[0063] Under the above-mentioned conditions, a silane-based gas containing, for example, Si as a predetermined element is supplied as the second gas to the wafer 200, whereby a Si-containing layer is formed on the wafer 200 as the second layer 306. Specifically, for example, on the inner surface of the recess 300, the second layer 306 is formed so that the density near the opening is lower than the density near the bottom (see FIG. 5(c)). The reason why the second layer 306 is formed with such a density distribution is that the Cl termination present on the surface of the first layer 304 acts as a factor, i.e., an inhibitor, that inhibits the adsorption of Si atoms contained in the second gas to the surface of the first layer 304.

[0064] After the second layer is formed, the valve 243b is closed to stop the supply of the second gas into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 (purging) by the same processing procedure and processing conditions as those for purging in step B.

[0065] The second gas may be, for example, the above-mentioned silane-based gas containing Si as the main element constituting the film formed on the wafer 200. The silane-based gas may be, for example, a gas containing Si and not containing halogen, such as monosilane (SiH4) gas or disilane (Si2H6) gas. One or more of these may be used as the second gas.

[0066] [Step E (Performing the film formation process and cycle a predetermined number of times)] By performing the cycle of the above-mentioned steps C and D non-simultaneously, i.e., without synchronization, a second predetermined number of times (m times, m being an integer of 1 or more), a film 308 formed by laminating the second layer 306, for example, a Si film, is formed on the wafer 200. As described above, for example, on the inner surface of the recess 300, the first layer 304 having the inhibitor effect has a higher density near the opening than near the bottom, so that the film 308 grows bottom-up from the bottom of the inner surface of the recess 300 toward the opening, and the recess 300 can be filled with the film 308 (see FIG. 5(d)). This allows a void-free and seamless film 308 to be formed in the recess 300, and the filling characteristics can be improved.

[0067] In the above-mentioned step D, for example, at least a part of Cl atoms (halogen atoms) in the Cl termination present on the surface of the first layer 304 may be detached from the surface of the first layer 304. As a result, the inhibitor effect of the first layer 304 may become insufficient, and the bottom-up growth of the film 308 may be inhibited. In this case, the first layer 304 whose surface is Cl-terminated can be formed again by performing the second predetermined number of times or more, that is, the above-mentioned cycle two or more times. As a result, the inhibitor effect of the first layer 304 can be maintained, and the bottom-up growth of the film 308 can be continued. As a result, the void-free and seamless film 308 can be formed in the recess 300, and the filling characteristics can be improved. Note that, when Cl atoms (halogen atoms) are detached from the surface of the first layer 304 in step D, the Si atoms (atoms of the specified element) constituting the first layer 304 that were bonded to the detached Cl atoms can be regarded as Si atoms (atoms of the specified element) constituting the film 308 as they are.

[0068] By performing the above-mentioned step D under conditions in which the second gas undergoes gas-phase decomposition (thermal decomposition), for example, Si contained in the second gas is deposited in multiple layers on the wafer 200. This can improve the formation rate of the film 308.

[0069] (After purging and atmospheric pressure recovery) After step E is completed, an inert gas is supplied as a purge gas from each of the nozzles 249a and 249b into the processing chamber 201 and exhausted from the exhaust port 231a. This purges the processing chamber 201, and gases and reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (after-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

[0070] (Boat unloading and wafer discharging) Thereafter, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafers 200 are carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the boat 217 (boat unloading). After the boat unloading, the shutter 219s is moved, and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). After being carried out to the outside of the reaction tube 203, the processed wafers 200 are taken out of the boat 217 (wafer discharge).

[0071] (3) Effects of this mode According to this aspect, one or more of the following effects can be obtained.

[0072] (a) The Cl termination present on the surface of the first layer 304 acts as an inhibitor that inhibits the formation of the second layer 306, so that, for example, when a recess 300 is formed on the surface of the wafer 200, the thickness distribution of the second layer 306 can be controlled by adjusting the density distribution of the first layer 304 in the recess 300. As a result, it becomes possible to form a film 308 with a desired thickness distribution in the recess 300.

[0073] Since the first gas contains Si like the second gas, the formation rate of the film 308 can be improved compared to a case where the first gas does not contain Si.

[0074] (b) In step C, since the density of the first layer 304 is higher near the opening than near the bottom on the inner surface of the recess 300, the film 308 grows bottom-up from the bottom of the inner surface of the recess 300 toward the opening, and the recess 300 is filled with the film 308. This allows a void-free and seamless film 308 to be formed in the recess 300, improving the filling characteristics.

[0075] (c) By using a non-H-containing gas as the first gas, it is possible to suppress the formation of a layer whose surface is terminated with H on the wafer 200. H atoms in an H-terminated layer are more likely to be desorbed from the layer than, for example, Cl atoms in a Cl-terminated layer. Therefore, when a layer whose surface is terminated with H is formed on the wafer 200, it may be difficult to exert the inhibitor effect in the first layer 304. By using a non-H-containing gas as the first gas, it is possible to suppress the formation of a layer whose surface is terminated with H, and therefore it is possible to fully exert the inhibitor effect in the first layer 304.

[0076] (d) By using a gas that does not contain bonds between Si atoms (Si-Si bonds) in one molecule as the first gas, it is possible to suppress the first gas from being thermally decomposed in step A. If the first gas is thermally decomposed, in step A, the Si contained in the first gas and adsorbed to the wafer 200 is likely to have dangling bonds. In step D, since the Si contained in the second gas may bond to these dangling bonds, the inhibitor effect of the first layer 304 may not be exerted. By using a gas that does not contain bonds between Si atoms in one molecule as the first gas, it is possible to fully exert the inhibitor effect of the first layer 304.

[0077] (e) After step C, at least until step D is started, a gas that reacts with the Cl termination and is different from both the first gas and the second gas is not supplied to the wafer 200, thereby suppressing the detachment of Cl atoms from the Cl termination present on the surface of the first layer 304. As a result, the first layer 304 maintains the presence of the Cl termination on the surface, and is therefore able to exert an inhibitor effect in step D.

[0078] (4) Variations The substrate processing sequence in this embodiment can be modified as shown in the following modified examples. These modified examples can be combined as desired. Unless otherwise specified, the process procedure and process conditions in each step of each modified example can be the same as the process procedure and process conditions in each step of the substrate processing sequence described above.

[0079] (Variation 1) As shown in the process sequence below, after performing a film formation process (step E), a process (step F) of supplying an etching gas capable of etching the film 308 to the wafer 200 may be performed, and then step E may be performed again. Both p and q shown below are integers of 1 or more.

[0080] [(first gas → purge) × n → second gas → purge] × m → etching gas → [(first gas → purge) × p → second gas → purge] × q

[0081] [Step F] In step F, an etching gas having an effect of etching the film 308 is supplied to the wafer 200 in the processing chamber 201, and a part of the film 308 is etched (removed).

[0082] Specifically, the valve 243c is opened to allow the etching gas to flow into the gas supply pipe 232c. The etching gas is adjusted in flow rate by the MFC 241c, supplied into the processing chamber 201 via the nozzle 249a, and exhausted from the exhaust port 231a. At this time, the etching gas is supplied to the wafer 200 (etching gas supply). At this time, the valves 243d and 243e may be opened to supply an inert gas into the processing chamber 201 via the nozzles 249a and 249b, respectively.

[0083] The processing conditions in this step are as follows: Treatment temperature: 200 to 800°C, preferably 300 to 600°C Treatment pressure: 10 to 100 kPa, preferably 100 to 50 kPa Etching gas supply flow rate: 0.01 to 10 slm, preferably 0.1 to 5 slm Etching gas supply time: 1 to 60 minutes, preferably 10 to 30 minutes The other processing conditions are the same as those in step A.

[0084] As the etching gas, for example, a halogen-containing gas such as chlorine (Cl2) gas, fluorine (F2) gas, chlorine trifluoride (ClF3) gas, hydrogen chloride (HCl) gas, hydrogen fluoride (HF) gas, etc. As the etching gas, one or more of these can be used.

[0085] In this modified example as well, the same effects as those of the above embodiment can be obtained.

[0086] By repeating the cycle including step C and step D, the vicinity of the opening of the recess 300 may be blocked by the film 308 before the inside of the recess 300 is completely filled with the film 308, resulting in a so-called overhang state. At this time, voids and seams extending in the depth direction may occur in the recess 300. In this modification, by supplying an etching gas to the wafer 200 under the above-mentioned conditions, a part of the film 308 formed in the vicinity of the opening in the recess 300 can be preferentially (selectively) removed. As a result, for example, before a void or seam is formed in the film 308 filled in the recess 300, the overhang state can be eliminated and the cycle including step C and step D can be continued. Also, for example, when a void or seam is formed in the film 308 filled in the recess 300, it is possible to eliminate these. After the voids and seams formed in the film 308 are eliminated, step E is further performed to reliably form a void-free and seamless film 308 in the recess 300, thereby further improving the filling characteristics.

[0087] Alternatively, a cycle of performing step E, then step F, and then performing step E again may be performed multiple times. This makes it possible to more reliably form a void-free and seamless film 308 in the recess 300 and further improve the filling characteristics.

[0088] (Variation 2) In step E, the first predetermined number of times during the cycle of steps C and D for forming film 308 near the opening of the inner surface of recess 300 may be less than the first predetermined number of times during the cycle of steps C and D for forming film 308 near the bottom of the inner surface of recess 300. As the film formation process (filling process) inside the recess 300 progresses, the aspect ratio of the recess 300 (depth of the recess / width of the recess) gradually decreases, so that the first layer 304 is likely to be formed at high density from the bottom of the recess 300 to the opening. This may reduce the formation rate of the second layer 306 throughout the recess 300, decreasing the productivity of the filling process. In addition, in a filling process performed in a state in which the first layer 304 is formed at high density from the bottom of the recess 300 to the opening, the thickness of the film 308 near the opening may be greater than the thickness of the film 308 near the bottom, which may cause voids and the like to occur in the recess 300, decreasing the productivity of the filling process. In this modification, the first layer 304 can be formed with a desired density distribution on the inner surface of the recess 300 by making the first predetermined number of cycles during the formation of the film 308 near the bottom of the inner surface of the recess 300, for example, during the early period of the filling process (during the first predetermined number of cycles in step E), smaller than the first predetermined number of cycles during the formation of the film 308 near the opening of the inner surface of the recess 300, for example, during the middle or final period of the filling process (during the last predetermined number of cycles in step E). This makes it possible to improve the filling characteristics of the film 308. It should be noted that the same effect can be obtained by decreasing the supply flow rate of the first gas per cycle in step C or by shortening the supply time of the first gas as the filling process progresses.

[0089] <Other Aspects of the Disclosure> Although the embodiments of the present disclosure have been specifically described above, the present disclosure is not limited to the above embodiments and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0090] In the above embodiment, bottom-up growth in which the film 308 is gradually formed from the bottom of the recess 300 toward the opening in step E has been described as an example, but the present disclosure is not limited to this. For example, the film 308 may be formed conformally to the inner surface of the recess 300. In these cases, the same effects as those of the above embodiment can be obtained.

[0091] In the above embodiment, the density of the first layer 304 near the opening of the inner surface of the recess 300 is made higher than the density of the first layer 304 near the bottom in step C, but the present disclosure is not limited to this. The density (dense / sparse) distribution of the first layer 304 in the recess 300 may be adjusted in any other desired manner. In these cases, the same effect as in the above embodiment can be obtained. In particular, a remarkable effect can be obtained when the film 308 is grown bottom-up or conformally formed, for example.

[0092] Although not specifically described in the above embodiment, the larger the aspect ratio of the recess 300, the more likely it is that an overhang state will occur, resulting in the generation of voids and the like within the recess 300. In the present disclosure, when the aspect ratio of the recess 300 is large, specifically, 10 or more, the effect of the above-mentioned filling characteristics can be significantly obtained.

[0093] In the above embodiment, the case where the surface of the first layer 304 is Cl-terminated has been described as an example, but the present disclosure is not limited thereto. For example, the surface of the first layer 304 may be F-terminated, Br-terminated, or I-terminated. In these cases, the same effects as those of the above embodiment can be obtained.

[0094] In the above-mentioned embodiment, the first gas is described by taking a silane-based gas containing Si as a predetermined element as an example, but the present disclosure is not limited thereto. For example, the first gas can be a gas containing a metalloid element such as boron (B), germanium (Ge), or arsenic (As) as a predetermined element. In addition, the first gas can be a gas containing a metal element such as titanium tetrachloride (TiCl4) gas containing titanium (Ti), zirconium tetrachloride (ZrCl4) gas containing zirconium (Zr), or hafnium tetrachloride (HfCl4) gas containing hafnium (Hf) as a predetermined element. In these cases, the same effect as the above-mentioned embodiment can be obtained.

[0095] It is preferable that the recipes used for each process are prepared individually according to the process contents, and are recorded and stored in the storage device 121c via an electric communication line or an external storage device 123. Then, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the process contents from among the multiple recipes recorded and stored in the storage device 121c. This makes it possible to form films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility using a single substrate processing device. It is also possible to reduce the burden on the operator, and to quickly start each process while avoiding operational errors.

[0096] The above-mentioned recipes may not only be created anew, but may also be prepared by modifying an existing recipe that has already been installed in the substrate processing apparatus. When modifying a recipe, the modified recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium on which the recipe has been recorded. In addition, an existing recipe that has already been installed in the substrate processing apparatus may be directly modified by operating the input / output device 122 provided in the existing substrate processing apparatus.

[0097] In the above-mentioned embodiment, an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at a time has been described. The present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a single-wafer type substrate processing apparatus that processes one or several substrates at a time. In addition, in the above-mentioned embodiment, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a substrate processing apparatus having a cold-wall type processing furnace.

[0098] When using these substrate processing apparatuses, each process can be performed using the same processing procedures and processing conditions as those in the above-mentioned aspects and modifications, and the same effects as those in the above-mentioned aspects and modifications can be obtained.

[0099] The above-mentioned aspects and modifications may be used in appropriate combination. The processing procedures and processing conditions in this case may be the same as those of the above-mentioned aspects. [Explanation of symbols]

[0100] 200 wafers (substrates) 304 1st layer 306 2nd layer 308 Membrane

Claims

1. (a) supplying a first gas containing a predetermined element and a halogen element to a substrate; (b) removing the first gas from the space in which the substrate resides; (c) performing a cycle including (a) and (b) a first predetermined number of times, which is at least two, to form a film on the substrate, forming a first layer containing the predetermined element and having a halogen-terminated surface; (d) applying a second gas, which is different from the first gas and contains the predetermined element, to the substrate on which the first layer is formed. forming a second layer containing the predetermined element on the substrate by supplying the predetermined element; (e) performing a cycle including (c) and (d) a second predetermined number of times to form a film containing the predetermined element on the substrate; A substrate processing method comprising the steps of:

2. (d) the halogen termination inhibits atoms of the predetermined element contained in the second gas from being adsorbed onto a surface of the first layer; The method of claim 1 .

3. The second predetermined number of times is two or more. The method of claim 1 .

4. The substrate has a recess on a surface thereof, the second predetermined number of times is the number of times the recess is filled with the film in (e); The substrate processing method according to claim 3 .

5. In (d), at least a portion of the halogen atoms in the halogen termination are eliminated from the first layer. The substrate processing method according to claim 3 or 4.

6. After (c), at least until (d) is started, a gas that reacts with the halogen termination and is different from both the first gas and the second gas is not supplied to the substrate. The method of claim 1 .

7. the first gas is a non-hydrogen containing gas; The method of claim 1 .

8. The first gas is a gas that does not contain bonds between atoms of the predetermined element in one molecule. The method of claim 1 .

9. (a) supplying a first gas containing a predetermined element and a halogen element to a substrate having a recess on a surface thereof; (b) removing the first gas from the space in which the substrate resides; (c) performing a cycle including steps (a) and (b) a first predetermined number of times to form a first layer on the substrate, the first layer containing the predetermined element and having a halogen-terminated surface; (d) supplying a second gas, which is different from the first gas and contains the predetermined element, to the substrate on which the first layer has been formed, to form a second layer containing the predetermined element on the substrate; (e) performing a cycle including (c) and (d) a second predetermined number of times to form a film containing the predetermined element on the substrate; In (c), a density of the first layer in a portion of the inner surface of the recess is made higher than a density of the first layer in another portion of the inner surface of the recess. A method for processing a substrate.

10. In (c), a density of the first layer in a vicinity of an opening of the inner surface of the recess is made higher than a density of the first layer in a vicinity of a bottom of the inner surface of the recess. The substrate processing method according to claim 9 .

11. In (e), the first predetermined number of times in (c) during the cycle of forming the film near the opening of the inner surface of the recess is made smaller than the first predetermined number of times in (c) during the cycle of forming the film near the bottom of the inner surface of the recess. The method of claim 10.

12. the execution time of (a) is a time during which a ratio of a density of the first layer formed in the vicinity of a bottom of the inner surface of the recess to a density of the first layer formed in the vicinity of an opening of the inner surface of the recess becomes a desired value; The substrate processing method according to claim 9 .

13. (a) is a supply flow rate of the first gas such that a ratio of a density of the first layer formed in the vicinity of a bottom of the inner surface of the recess to a density of the first layer formed in the vicinity of an opening of the inner surface of the recess becomes a desired value. The substrate processing method according to claim 9 .

14. (d) is carried out under conditions in which the second gas undergoes gas-phase decomposition; The method of claim 1 .

15. (f) removing a portion of the film by supplying an etching gas to the substrate on which the film is formed; The method of claim 1 .

16. After (f), further performing (e); performing a cycle including (e) and (f) a plurality of times; The method of claim 15.

17. (a) supplying a first gas containing a predetermined element and a halogen element to a substrate; (b) removing the first gas from the space in which the substrate resides; (c) performing a cycle including (a) and (b) a first predetermined number of times, which is two or more, to form a first layer on the substrate, the first layer containing the predetermined element and having a halogen-terminated surface; (d) supplying a second gas, which is different from the first gas and contains the predetermined element, to the substrate on which the first layer has been formed, to form a second layer containing the predetermined element on the substrate; (e) performing a cycle including (c) and (d) a second predetermined number of times to form a film containing the predetermined element on the substrate; A method for manufacturing a semiconductor device having the above structure.

18. (a) supplying a first gas containing a predetermined element and a halogen element to a substrate; (b) removing the first gas from a space in which the substrate resides; and (c) performing a cycle including steps (a) and (b) a first predetermined number of times, which is at least two, to form a first layer on the substrate, the first layer containing the predetermined element and having a halogen-terminated surface; (d) supplying a second gas, which is different from the first gas and contains the predetermined element, to the substrate on which the first layer has been formed, to form a second layer containing the predetermined element on the substrate; (e) performing a cycle including steps (c) and (d) a second predetermined number of times to form a film containing the predetermined element on the substrate; and A program for causing a computer to execute the above in a substrate processing apparatus.

19. a first gas supply system that supplies a first gas containing a predetermined element and a halogen element to the substrate; an exhaust system for removing the first gas from a space in which the substrate is present; a second gas supply system that supplies a second gas, which is different from the first gas and contains the predetermined element, to the substrate; a control unit configured to be capable of controlling the first gas supply system, the exhaust system, and the second gas supply system to perform the following processes: (a) a process of supplying the first gas to the substrate; (b) a process of removing the first gas from a space in which the substrate exists; (c) a process of forming a first layer containing the predetermined element and having a halogen-terminated surface on the substrate by performing a cycle including (a) and (b) a first predetermined number of times, which is two or more; (d) a process of supplying the second gas to the substrate on which the first layer has been formed, to form a second layer containing the predetermined element on the substrate; and (e) a process of forming a film containing the predetermined element on the substrate by performing a cycle including (c) and (d) a second predetermined number of times. A substrate processing apparatus comprising:

20. The method of claim 1, further comprising: (a) supplying a first gas containing a predetermined element and a halogen element to a substrate having a recess on a surface thereof; (b) removing the first gas from the space in which the substrate resides; (c) performing a cycle including steps (a) and (b) a first predetermined number of times to form a first layer on the substrate, the first layer containing the predetermined element and having a halogen-terminated surface; (d) supplying a second gas, which is different from the first gas and contains the predetermined element, to the substrate on which the first layer has been formed, to form a second layer containing the predetermined element on the substrate; (e) performing a cycle including (c) and (d) a second predetermined number of times to form a film containing the predetermined element on the substrate; having In (c), a density of the first layer in a portion of the inner surface of the recess is made higher than a density of the first layer in another portion of the inner surface of the recess. A method for manufacturing a semiconductor device.

21. The method of claim 20, further comprising the steps of: (a) supplying a first gas containing a predetermined element and a halogen element to a substrate having a recess on a surface thereof; (b) removing the first gas from a space in which the substrate resides; and (c) performing a cycle including steps (a) and (b) a first predetermined number of times to form a first layer on the substrate, the first layer containing the predetermined element and having a halogen-terminated surface; (d) supplying a second gas, which is different from the first gas and contains the predetermined element, to the substrate on which the first layer has been formed, to form a second layer containing the predetermined element on the substrate; (e) performing a cycle including steps (c) and (d) a second predetermined number of times to form a film containing the predetermined element on the substrate; and Including, (c) making a density of the first layer in a portion of the inner surface of the recess higher than a density of the first layer in another portion of the inner surface of the recess, A program that is executed by a computer in a substrate processing apparatus.

22. A first gas supply system that supplies a first gas containing a predetermined element and a halogen element to a substrate having a recess on a surface thereof; an exhaust system for removing the first gas from a space in which the substrate is present; a second gas supply system that supplies a second gas, which is different from the first gas and contains the predetermined element, to the substrate; (a) a process of supplying the first gas to the substrate; (b) a process of removing the first gas from a space in which the substrate exists; (c) a process of forming a first layer containing the predetermined element and having a halogen-terminated surface on the substrate by performing a cycle including (a) and (b) a first predetermined number of times; (d) a process of supplying the second gas to the substrate on which the first layer has been formed, to form a second layer containing the predetermined element on the substrate; and (e) a process of forming a film containing the predetermined element on the substrate by performing a cycle including (c) and (d) a second predetermined number of times, wherein in (c), a control unit configured to be able to control the first gas supply system, the exhaust system, and the second gas supply system to cause a process of making the density of the first layer in a portion of the inner surface of the recess higher than the density of the first layer in another portion of the inner surface of the recess to be performed. A substrate processing apparatus comprising:

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