Processing method, semiconductor device manufacturing method, processing apparatus, and program

Abstract

Provided is a processing method for performing a cycle including: (a) a step for adsorbing at least a part of X in the molecular structure of molecules constituting a first substance at the upper part inside a recess by supplying the first substance, which contains a first element and does not contain chlorine, to a substrate having the recess on the surface thereof; (b) a step for forming a first layer by supplying a chlorine-free second substance containing the first element to the substrate and adsorbing at least a portion of Y in the molecular structure of molecules constituting the second substance in a non-adsorbed portion of X in the recess; and (c) a step for modifying the first layer into a second layer by supplying a third substance containing a second element different from the first element to the substrate.

Description

Technical Field

[0001] The present disclosure relates to a processing method, a method for manufacturing a semiconductor device, a processing device, and a program. Background Art

[0002] As one of the steps in the process of manufacturing a semiconductor device, a process of forming a film in a recessed portion such as a groove or a hole provided on a surface of a substrate is sometimes performed (for example, see Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2017-069407 Summary of the invention

[0006] Problems to be solved by the invention

[0007] As semiconductor devices become smaller, there is a strong demand for improving properties such as step coverage of a film formed in a recessed portion.

[0008] The present disclosure provides a technology capable of improving the characteristics of a film formed in a concave portion.

[0009] Methods for solving problems

[0010] According to one embodiment of the present disclosure, there is provided a technique comprising a step of forming a film containing the first element and the second element in the concave portion by performing a cycle including the following (a), (b), and (c) n times (n is an integer greater than or equal to 1 or 2),

[0011] (a) supplying a first substance containing a first element and not containing chlorine to a substrate having a concave portion on its surface, thereby adsorbing at least a portion X of a molecular structure of molecules constituting the first substance at an upper portion of the concave portion;

[0012] (b) a step of supplying a second substance containing the first element and not containing chlorine to the substrate, thereby adsorbing at least a portion Y of the molecular structure of molecules constituting the second substance at the non-adsorbed portion of X in the recessed portion to form a first layer; and

[0013] (c) a step of supplying a third substance containing a second element different from the first element to the substrate to modify the first layer into a second layer,

[0014] (c) is performed under processing conditions in which the film is formed at a first film forming rate when the second substance and the third substance are alternately supplied, and under processing conditions in which the film is formed at a second film forming rate lower than the first film forming rate when the first substance and the third substance are alternately supplied; or (c) is performed under processing conditions in which the film is formed at a first film forming rate when the second substance and the third substance are alternately supplied, and under processing conditions in which the film is not substantially formed when the first substance and the third substance are alternately supplied.

[0015] Effects of the Invention

[0016] According to the present disclosure, the characteristics of the film formed in the recessed portion can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] [ Figure 1 ] Figure 1 It is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus that is preferably used in one embodiment of the present disclosure, and is a diagram showing a processing furnace 202 portion in a vertical cross-sectional view.

[0018] [ Figure 2 ] Figure 2 This is a schematic diagram of a vertical processing furnace of a substrate processing device suitable for use in one embodiment of the present invention. Figure 1 The AA line cross-sectional view shows a portion of the processing furnace 202 .

[0019] [ Figure 3 ] Figure 3 1 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus that is preferably used in one embodiment of the present disclosure, and is a diagram showing a control system of the controller 121 in the form of a block diagram.

[0020] [ Figure 4 ] Figure 4 This is a diagram showing a processing sequence in one embodiment of the present disclosure.

[0021] [ Figure 5 ] Figure 5 (a) is a schematic cross-sectional view showing a portion of a wafer surface after supplying a first substance to a wafer having a concave portion on its surface; Figure 5 (b) is displayed by Figure 5 (a), a schematic cross-sectional view of a portion of the wafer surface after the second substance is supplied to the wafer; Figure 5 (c) is displayed by Figure 5 (b) is a schematic cross-sectional view of a portion of a wafer surface after supplying the third substance to the wafer under the processing conditions of forming a film at a first film forming rate when the second substance and the third substance are alternately supplied, and under the processing conditions of substantially not forming a film when the first substance and the third substance are alternately supplied; Figure 5(d) is displayed by Figure 5 (c) is a schematic cross-sectional view of a portion of the wafer surface after the wafer has been subjected to an n-th cycle of the film forming step; Figure 5 (e) is displayed by Figure 5 (d) is a schematic cross-sectional view of the surface portion of the wafer after the modifier is supplied to the wafer.

[0022] [ Figure 6 ] Figure 6 (a) is a schematic cross-sectional view showing a portion of a wafer surface after supplying a first substance to a wafer having a concave portion on its surface; Figure 6 (b) is displayed by Figure 6 (a), a schematic cross-sectional view of a portion of the wafer surface after the second substance is supplied to the wafer; Figure 6 (c) is displayed by Figure 6 (b), a schematic cross-sectional view of a portion of a wafer surface after supplying the third substance to the wafer under the processing conditions of forming a film at a first film forming rate when the second substance and the third substance are alternately supplied, and forming a film at a second film forming rate lower than the first film forming rate when the first substance and the third substance are alternately supplied; Figure 6 (d) is displayed by Figure 6 (c) is a schematic cross-sectional view of a portion of the wafer surface after the wafer has been subjected to an n-th cycle of the film forming step. DETAILED DESCRIPTION

[0023] <One aspect of the present disclosure>

[0024] Hereinafter, for one aspect of the present disclosure, reference will be made mainly to Figure 1 to Figure 4 , Figure 5 (a)~ Figure 5 (d) Description. It should be noted that the drawings used in the following description are schematic diagrams, and the dimensional relationship of each element, the ratio of each element, etc. shown in the drawings do not necessarily have to be consistent with reality. In addition, the dimensional relationship of each element, the ratio of each element, etc. between multiple drawings do not necessarily have to be the same.

[0025] (1) Configuration of the processing device

[0026] like Figure 1 As shown, the processing furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and supported by a holding plate so as to be vertically installed. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) the gas using heat.

[0027] On the inner side of the heater 207, a reaction tube 203 is arranged concentrically with 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 into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS), and is formed into a cylindrical shape with an upper end and a lower end open. The upper end of the manifold 209 cooperates with the lower end of the reaction tube 203 to support the reaction tube 203. An O-ring 220a as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically in the same manner as the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing container (reaction container). The processing chamber 201 is formed in the hollow portion of the cylinder of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. The wafer 200 is processed in the processing chamber 201 .

[0028] In the processing chamber 201, nozzles 249a to 249c are respectively provided as first to third supply parts in a manner penetrating the side wall of the manifold 209. The nozzles 249a to 249c are also respectively referred to as first to third nozzles. The nozzles 249a to 249c are made of, for example, a heat-resistant material such as quartz or SiC. The nozzles 249a to 249c are respectively connected to the gas supply pipes 232a to 232c. The nozzles 249a to 249c are different nozzles, and the nozzles 249a and 249c are respectively provided adjacent to the nozzle 249b.

[0029] In the gas supply pipes 232a to 232c, mass flow controllers (MFC) 241a to 241c as flow controllers (flow control units) and valves 243a to 243c as opening and closing valves are provided in order from the upstream side of the gas flow. A gas supply pipe 232d is connected to the downstream side of the valve 243a of the gas supply pipe 232a. A gas supply pipe 232e is connected to the downstream side of the valve 243b of the gas supply pipe 232b. A gas supply pipe 232f is connected to the downstream side of the valve 243c of the gas supply pipe 232c. In the gas supply pipes 232d to 232f, MFCs 241d to 241f and valves 243d to 243h are provided in order from the upstream side of the gas flow. The gas supply pipes 232a to 232f are made of metal materials such as SUS, for example.

[0030] like Figure 2As shown, the nozzles 249a to 249c are respectively arranged in a circular ring-shaped space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, so as to stand upright from the lower part of the inner wall of the reaction tube 203 along the upper part toward the arrangement direction of the wafer 200. That is, the nozzles 249a to 249c are respectively arranged in a region that horizontally surrounds the wafer arrangement region on the side of the wafer arrangement region where the wafers 200 are arranged, and along the wafer arrangement region. In a plan view, the nozzle 249b is arranged so as to face the exhaust port 231a described later on a straight line with the center of the wafer 200 carried into the processing chamber 201 sandwiched therebetween. The nozzles 249a and 249c are arranged so as to sandwich a straight line L connecting the center of the nozzle 249b and the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer periphery of the wafer 200). The straight line L is also a straight line connecting the nozzle 249b and the center of the wafer 200. That is, it can also be said that the nozzle 249c is arranged on the opposite side of the nozzle 249a with the straight line L sandwiched therebetween. The nozzles 249a and 249c are arranged to be line symmetrical with the straight line L as the axis of symmetry. On the side surfaces of the nozzles 249a to 249c, gas supply holes 250a to 250c for supplying gas are respectively provided. The gas supply holes 250a to 250c are respectively opened in a manner opposite to (face to face with) the exhaust port 231a in a plan view, and can supply gas to the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the lower part to the upper part of the reaction tube 203.

[0031] The first substance containing the first element and not containing chlorine is supplied from the gas supply pipe 232 a into the processing chamber 201 via the MFC 241 a , the valve 243 a , and the nozzle 249 a .

[0032] The second substance containing the first element and not containing chlorine is supplied from the gas supply pipe 232 b into the processing chamber 201 via the MFC 241 b , the valve 243 b , and the nozzle 249 b .

[0033] The third substance containing the second element different from the first element is supplied from the gas supply pipe 232 c through the MFC 241 c , the valve 243 c , and the nozzle 249 c into the processing chamber 201 .

[0034] The inert gas is supplied from the gas supply pipes 232d to 232f into the processing chamber 201 via the MFCs 241d to 241f, valves 243d to 243f, gas supply pipes 232a to 232c, and nozzles 249a to 249c. The inert gas functions as a purge gas, a carrier gas, a dilution gas, and the like.

[0035] The first material supply system is mainly composed of the gas supply pipe 232a, MFC241a, and valve 243a. The second material supply system is mainly composed of the gas supply pipe 232b, MFC241b, and valve 243b. The third material supply system is mainly composed of the gas supply pipe 232c, MFC241c, and valve 243c. The inert gas supply system is mainly composed of the gas supply pipes 232d to 232f, MFC241d to 241f, and valves 243d to 243f.

[0036] Any or all of the above-mentioned various supply systems can also be configured as an integrated supply system 248 formed by integrating valves 243a~243f, MFC241a~241f, etc. The integrated supply system 248 is configured to be connected to each gas supply pipe 232a~232f, and the operation of supplying various substances (various gases) into the gas supply pipe 232a~232f, that is, the opening and closing operation of the valves 243a~243f, the flow rate adjustment operation performed by the MFC241a~241f, etc., is controlled by the controller 121 described later. The integrated supply system 248 is configured in the form of an integrated unit of an integral type or a split type, and is configured to be able to install and remove the gas supply pipes 232a~232f, etc. as an integrated unit, and to be able to perform maintenance, replacement, and additional installation of the integrated supply system 248 as an integrated unit.

[0037] An exhaust port 231a is provided below the side wall of the reaction tube 203 to exhaust the atmosphere in the processing chamber 201. Figure 2 As shown, the exhaust port 231a is provided at a position opposite (face to face) to the nozzles 249a to 249c (gas supply holes 250a to 250c) sandwiching the wafer 200 in a plan view. The exhaust port 231a can be provided from the lower part of the side wall of the reaction tube 203 along the upper part, that is, along the wafer arrangement area. The exhaust port 231a is connected to the exhaust pipe 231. The exhaust pipe 231 is connected to the vacuum pump 246 as a vacuum exhaust device via the pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and the APC (Auto Pressure Controller, pressure automatic regulator) valve 244 as a pressure regulator (pressure regulating unit). The APC valve 244 is configured to open and close the valve in a state where the vacuum pump 246 is operated, so that the vacuum exhaust in the processing chamber 201 can be performed and the vacuum exhaust can be stopped. Furthermore, in a state where the vacuum pump 246 is operated, the pressure in the processing chamber 201 can be adjusted by adjusting the valve opening based on the pressure information detected by the pressure sensor 245. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 can also be included in the exhaust system.

[0038] Below the manifold 209, there is provided a sealing cap 219 as a furnace cover capable of hermetically closing the lower end opening of the manifold 209. The sealing cap 219 is made of a metal material such as SUS and is formed into a disc shape. On the upper surface of the sealing cap 219, there is provided an O-ring 220b as a sealing member that abuts against the lower end of the manifold 209. Below the sealing cap 219, there is provided a rotating mechanism 267 for rotating the wafer box 217 described later. The rotating shaft 255 of the rotating mechanism 267 passes through the sealing cap 219 and is connected to the wafer box 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer box 217. The sealing cap 219 is configured to be lifted and lowered in the vertical direction by the wafer box elevator 115 as a lifting mechanism provided outside the reaction tube 203. The cassette elevator 115 is configured as a transport device (transport mechanism) that carries the wafer 200 in and out (transports) the wafer 200 in and out of the processing chamber 201 by raising and lowering the sealing cap 219 .

[0039] A baffle 219s is provided below the manifold 209 as a furnace cover, and when the sealing cap 219 is lowered and the wafer box 217 is carried out from the processing chamber 201, the lower end opening of the manifold 209 can be airtightly closed. The baffle 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c as a sealing member that abuts against the lower end of the manifold 209 is provided on the upper surface of the baffle 219s. The opening and closing actions (lifting and lowering actions, rotating actions, etc.) of the baffle 219s are controlled by the baffle switch mechanism 115s.

[0040] The wafer box 217 as a substrate support is configured to support multiple (e.g., 25 to 200) wafers 200 in a horizontal position and aligned with each other's centers in a vertical direction in multiple stages, that is, arranged at intervals. The wafer box 217 is made of, for example, a heat-resistant material such as quartz or SiC. At the bottom of the wafer box 217, a heat insulation plate 218 made of, for example, a heat-resistant material such as quartz or SiC is supported in multiple stages.

[0041] A temperature sensor 263 as a temperature detector is provided in the reaction tube 203. The temperature in the processing chamber 201 is set to a desired temperature distribution by adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0042] like Figure 3As shown, the controller 121 as a control unit (control unit) is configured as a computer having a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O interface 121d. The RAM 121b, the storage device 121c, and the I / O interface 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. The controller 121 is connected to an input / output device 122 configured as, for example, a touch panel. In addition, the controller 121 can be connected to an external storage device 123. In addition, the processing device can be configured to have one control unit or multiple control units. That is, the control for the processing sequence described later can be performed using one control unit or multiple control units. In addition, the multiple control units can also be configured as a control system connected to each other through a wired or wireless communication network, and the control for the processing sequence described later can also be performed by the control system as a whole. When the term "control unit" is used in this specification, it may include a case where a plurality of control units are included, or a control system composed of a plurality of control units is included, in addition to the case where one control unit is included.

[0043] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. In the storage device 121c, a control program for controlling the action of the substrate processing device, a process recipe that records the steps and conditions of the substrate processing described later, etc., are recorded and stored in a readable form. The process recipe is composed in a manner that the processing device uses the controller 121 to execute the various steps of the substrate processing described later and can obtain the predetermined results, and functions as a program. Hereinafter, the process recipe, control program, etc. are also simply referred to as a program. In addition, the process recipe is also simply referred to as a recipe. When the term "program" is used in this specification, there are cases where only the recipe is included, only the control program is included, or both are included. RAM121b is configured as a storage area (working area) for temporarily storing programs, data, etc. read by CPU121a.

[0044] The I / O interface 121d is connected to the above-mentioned MFC241a~241f, valves 243a~243f, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, wafer box elevator 115, shutter switch mechanism 115s, etc.

[0045] The CPU 121a is configured to read out a control program from the storage device 121c and execute it, and to read out a recipe from the storage device 121c based on input of an operation command from the input / output device 122. The CPU 121a is configured to control, according to the contents of the read recipe, the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241f, the opening and closing operation of the valves 243a to 243f, the opening and closing operation of the APC valve 244 and the pressure adjustment operation of 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 wafer box 217 by the rotation mechanism 267, the lifting and lowering operation of the wafer box 217 by the wafer box elevator 115, the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, and the like.

[0046] The controller 121 can be constructed by installing the above-mentioned program recorded and stored in the external storage device 123 into the computer. The external storage device 123 includes, for example, magnetic disks such as HDD, optical disks such as CD, optical magnetic disks such as MO, USB memory, semiconductor memory such as SSD, etc. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, they are also simply collectively referred to as recording media. When the term "recording medium" is used in this specification, there are situations where only the storage device 121c is included alone, only the external storage device 123 is included alone, or both are included. It should be noted that providing a program to a computer can also be done without using the external storage device 123, but by using communication means such as the Internet and dedicated lines.

[0047] (2) Processing

[0048] The substrate processing apparatus is used as a process in the manufacturing process of a semiconductor device. Figure 4 , Figure 5 (a)~ Figure 5 (d) A method for processing a substrate, that is, an example of a processing sequence for forming a film in a groove, hole or other concave portion provided on the surface of a wafer 200 as a substrate, is described. In the following description, the operation of each part constituting the processing device is controlled by the controller 121. It should be noted that the processing device is also referred to as a substrate processing device, a film forming processing device or a film forming device. In addition, the processing method is also referred to as a substrate processing method, a film forming processing method or a film forming method.

[0049] In the processing sequence of this embodiment, a step (film forming step) of forming a film containing the first element and the second element in the concave portion is performed by performing a cycle including the following (a), (b) and (c) n times (n is an integer greater than or equal to 1 or 2),

[0050] (a) supplying a first substance containing a first element and not containing chlorine to a wafer 200 having a recess on its surface, thereby adsorbing at least a portion X of a molecular structure constituting a molecule of the first substance at an upper portion of the recess (first substance supplying step);

[0051] (b) supplying a second substance containing the first element and not containing chlorine to the wafer 200, thereby adsorbing at least a portion Y of the molecular structure of the molecules constituting the second substance to the non-adsorbed portion of X in the recess to form a first layer (second substance supplying step); and

[0052] (c) supplying a third substance containing a second element different from the first element to the wafer 200 so as to modify the first layer into the second layer (third substance supplying step),

[0053] The third substance supplying step is performed under processing conditions in which a film is formed at a first film forming rate while the second substance and the third substance are alternately supplied, and under processing conditions in which a film is formed at a second film forming rate lower than the above-mentioned first film forming rate while the first substance and the third substance are alternately supplied, or under processing conditions in which substantially no film is formed.

[0054] Hereinafter, a case where the third substance supplying step is performed under the processing conditions that a film is formed at a first film formation rate when the second substance and the third substance are alternately supplied, and under the processing conditions that substantially no film is formed when the first substance and the third substance are alternately supplied.

[0055] In this specification, for convenience, the above-mentioned processing sequence may be expressed as follows. The same description is also used in the following description of modified examples, other aspects, etc.

[0056] (first substance→second substance→third substance)×n

[0057] In this specification, when the term "wafer" is used, it includes the meaning of the wafer itself, and the meaning of a stack of a wafer and a predetermined layer or film formed on its surface. When the term "wafer surface" is used in this specification, it includes the meaning of the surface of the wafer itself, and the meaning of the surface of a predetermined layer formed on the wafer. In this specification, when it is recorded as "forming a predetermined layer on the wafer", it includes the meaning of directly forming the predetermined layer on the surface of the wafer itself, and the meaning of forming the predetermined layer 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.

[0058] The term "substance" used in this specification includes at least one of a gaseous substance and a liquid substance. A liquid substance includes a mist substance. That is, each of the first substance, the second substance, and the third substance may include a gaseous substance, a liquid substance such as a mist substance, or both.

[0059] The term "layer" used in this specification includes at least one of a continuous layer and a discontinuous layer. For example, the first layer and the second layer may each include a continuous layer, a discontinuous layer, or both.

[0060] (Wafer loading and wafer cassette loading)

[0061] After a plurality of wafers 200 are loaded into the wafer box 217 (wafer loading), the shutter 219s is moved by the shutter opening and closing mechanism 115s to open the lower end opening of the manifold 209 (shutter opening). Figure 1 As shown, the wafer cassette 217 supporting a plurality of wafers 200 is lifted by the wafer cassette elevator 115 and carried into the processing chamber 201 (wafer cassette loading). In this state, the sealing cap 219 seals the lower end of the manifold 209 via the O-ring 220b. In this way, the wafers 200 are prepared (provided) in the processing chamber 201.

[0062] (Pressure regulation and temperature regulation)

[0063] After the wafer box is loaded, the vacuum pump 246 performs vacuum exhaust (decompression exhaust) so that the space in the processing chamber 201 where the wafer 200 exists reaches the desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback controlled based on the measured pressure information. In addition, the heater 207 heats the wafer 200 in the processing chamber 201 so that it reaches the desired temperature. At this time, the power supply of the heater 207 is feedback controlled based on the temperature information detected by the temperature sensor 263 so that the desired temperature distribution is achieved in the processing chamber 201. In addition, the rotation mechanism 267 starts to rotate the wafer 200. The exhaust in the processing chamber 201, the heating and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.

[0064] (Film Forming Step)

[0065] Thereafter, the first substance supplying step, the second substance supplying step, and the third substance supplying step are sequentially performed.

[0066] [First substance supply step]

[0067] In this step, a first substance containing a first element and not containing chlorine (Cl) is supplied to the wafer 200 having a recessed portion on the surface.

[0068] Specifically, valve 243a is opened to allow the first substance to flow into gas supply pipe 232a. The first substance is flow-regulated by MFC 241a, supplied to processing chamber 201 via nozzle 249a, and exhausted by exhaust port 231a. At this time, the first substance is supplied to wafer 200 from the side of wafer 200 (first substance supply). At this time, valves 243d to 243f may also be opened to supply inactive gas to processing chamber 201 via nozzles 249a to 249c, respectively.

[0069] By supplying the first substance to the wafer 200 under the following processing conditions, Figure 5 As shown in (a), X, which is at least a part of the molecular structure of the molecule constituting the first substance, can be adsorbed at the upper part of the concave portion on the surface of the wafer 200. At this time, it is preferable to supply the first substance slightly insufficiently to the wafer 200 under the condition that the adsorption of X into the concave portion becomes non-saturated, that is, under the condition that the adsorption of X into the concave portion does not self-limit. For example, by making the supply time of the first substance shorter than the supply time of the second substance, the supply of the first substance slightly insufficiently to the wafer 200 can be achieved. It should be noted that the processing conditions shown below include the condition that the adsorption of X into the concave portion becomes non-saturated.

[0070] As the processing conditions when the first substance is supplied in the first substance supplying step, the following can be exemplified:

[0071] Treatment temperature: room temperature (25°C) to 800°C, preferably 400 to 650°C

[0072] Processing pressure: 1-2000 Pa, preferably 1-1000 Pa

[0073] First material supply flow rate: 0.001 to 3 slm, preferably 0.001 to 0.5 slm

[0074] First material supply time: 0.1 to 60 seconds, preferably 0.1 to 30 seconds

[0075] Inert gas supply flow rate (per gas supply pipe): 0~20slm

[0076] It should be noted that the description of a numerical range such as "1 to 2000Pa" in this specification means that the lower limit and the upper limit are included in the range. Therefore, for example, "1 to 2000Pa" means "above 1Pa and below 2000Pa". The same applies to other numerical ranges. In addition, the processing temperature in this specification refers to the temperature of the wafer 200 or the temperature in the processing chamber 201, and the processing pressure refers to the pressure in the processing chamber 201. In addition, the processing time refers to the duration of the processing. In addition, the supply flow rate includes a case of 0slm, and 0slm means a case where the substance (gas) is not supplied. These are also the same in the following descriptions.

[0077] As the first substance, for example, a substance containing a partial structure in which the first element, an amino group, and an alkyl group are bonded, or a substance containing a partial structure in which the first element, an amino group, and hydrogen are bonded can be used. When these substances are used as the first substance, X adsorbed on the upper part of the concave portion can contain at least any one of a chemical bond between the first element and an alkyl group, a chemical bond between the first element and hydrogen, and a chemical bond between the first element and an amino group. That is, X can contain at least any one of the first element and an alkyl group, hydrogen, and an amino group.

[0078] The first element contains silicon (Si), for example. At this time, as the first substance, for example, the following substances can be used: a substance containing one or more chemical bonds between the first element and an alkyl group and three or less chemical bonds between the first element and an amino group in one molecule; or a substance containing one or more chemical bonds between the first element and hydrogen and three or less chemical bonds between the first element and an amino group in one molecule. The "one or more" and "three or less" mentioned here do not mean the number of the first element, but the number of chemical bonds. It should be noted that in the present disclosure, the chemical bond between the first element and the alkyl group refers to the bond between the first element and the carbon (C) constituting the alkyl group. In addition, the chemical bond between the first element and the amino group refers to the bond between the first element and the nitrogen (N) constituting the amino group.

[0079] As the first substance, for example, (dialkylamino)trialkylsilane such as (dimethylamino)trimethylsilane ((CH3)2NSi(CH3)3) containing three chemical bonds between the first element and an alkyl group and one chemical bond between the first element and an amino group in one molecule can be used.

[0080] In addition, as the first substance, for example, bis(dialkylamino)dialkylsilane such as bis(dimethylamino)dimethylsilane ([(CH3)2N]2Si(CH3)2) which contains two chemical bonds between the first element and an alkyl group and two chemical bonds between the first element and an amino group in one molecule can be used.

[0081] In addition, as the first substance, tri(dialkylamino)alkylsilane such as tri(dimethylamino)methylsilane ([(CH3)2N]3SiCH3) which contains one chemical bond between the first element and an alkyl group and three chemical bonds between the first element and an amino group in one molecule can be used.

[0082] In addition, as the first substance, mono(dialkylamino)silanes such as (diisobutylamino)silane ((C4H9)2NSiH3) and (diisopropylamino)silane ((C3H7)2NSiH3) which contain three chemical bonds between the first element and hydrogen and one chemical bond between the first element and an amino group in one molecule can be used.

[0083] In addition, as the first substance, for example, bis(dialkylamino)silanes such as bis(diethylamino)silane ([(C2H5)2N]2SiH2) and bis(monoalkylamino)silanes such as bis(tert-butylamino)silane ([(C4H9)NH]2SiH2) that contain two chemical bonds between the first element and hydrogen and two chemical bonds between the first element and amino groups in one molecule can be used.

[0084] In addition, as the first substance, tri(dialkylamino)silane such as tri(dimethylamino)silane ([(CH3)2N]3SiH) which contains one chemical bond between the first element and hydrogen and three chemical bonds between the first element and amino groups in one molecule can be used.

[0085] As the first substance, one or more of these can be used. It should be noted that the "1", "2" and "3" mentioned above do not mean the number of the first element but the number of chemical bonds.

[0086] As the inert gas, for example, rare gases such as nitrogen (N2) gas, argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas can be used. As the inert gas, one or more of these can be used. This also applies to each step described later.

[0087] After X is adsorbed at the upper part of the concave portion on the surface of the wafer 200, the valve 243a is closed to stop the supply of the first substance into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove the gaseous substances remaining in the processing chamber 201 from the processing chamber 201. At this time, the valves 243d to 243f are opened, and an inert gas is supplied to the processing chamber 201 through the nozzles 249a to 249c. The inert gas supplied by the nozzles 249a to 249c acts as a purge gas, thereby purging (purging) the processing chamber 201. The processing temperature during the purge in this step is preferably set to the same temperature as the processing temperature when the first substance is supplied.

[0088] [Second substance supply step]

[0089] After the first substance supplying step is completed, the second substance containing the first element and not containing chlorine (Cl) is supplied to the wafer 200 , that is, to the wafer 200 after X is adsorbed on the upper portion of the concave portion of the surface.

[0090] Specifically, valve 243b is opened to allow the second substance to flow into gas supply pipe 232b. The second substance is flow-regulated by MFC241b, supplied to processing chamber 201 via nozzle 249b, and exhausted by exhaust port 231a. At this time, the second substance is supplied to wafer 200 from the side of wafer 200 (second substance supply). At this time, valves 243d to 243f may also be opened to supply inactive gas to processing chamber 201 via nozzles 249a to 249c, respectively.

[0091] By supplying the second substance to the wafer 200 under the following processing conditions, Figure 5 As shown in (b), Y, which is at least a part of the molecular structure of the molecules constituting the second substance, can be adsorbed in the non-adsorbed portion of X in the concave portion on the surface of the wafer 200 to form a first layer. The first layer becomes a layer containing the first element. It should be noted that the non-adsorbed portion of X in the concave portion includes the bottom, lower part and central part of the concave portion.

[0092] As the processing conditions when the second substance is supplied in the second substance supplying step, the following can be exemplified:

[0093] Treatment temperature: room temperature (25°C) to 800°C, preferably 400 to 650°C

[0094] Processing pressure: 1-2000 Pa, preferably 1-1000 Pa

[0095] Second material supply flow rate: 0.001 to 3 slm, preferably 0.001 to 0.5 slm

[0096] Second material supply time: 1 to 120 seconds, preferably 1 to 60 seconds

[0097] Inert gas supply flow rate (per gas supply pipe): 0~20slm

[0098] As the second substance, for example, a substance containing a partial structure in which the first element is bonded to an amino group and an alkoxy group can be used. When such a substance is used as the second substance, Y in the non-adsorbed portion of X adsorbed in the concave portion can contain at least one of a chemical bond between the first element and an alkoxy group and a chemical bond between the first element and an amino group. That is, X can contain at least one of the first element and an alkoxy group and an amino group.

[0099] The first element contains Si, for example, as described above. At this time, as the second substance, for example, a substance containing one or more chemical bonds between the first element and an alkoxy group, and three or less chemical bonds between the first element and an amino group in one molecule can be used. The "one or more" and "three or less" mentioned here do not mean the number of the first element, but refer to the number of chemical bonds. It should be noted that in the present disclosure, the chemical bond between the first element and the alkoxy group refers to the bond between the first element and the oxygen (O) constituting the alkoxy group. In addition, the chemical bond between the first element and the amino group refers to the bond between the first element and the N constituting the amino group as described above.

[0100] As the second substance, for example, (dialkylamino)trialkoxysilane such as (dimethylamino)trimethoxysilane ((CH3)2NSi(OCH3)3) containing three chemical bonds between the first element and an alkoxy group and one chemical bond between the first element and an amino group in one molecule can be used.

[0101] In addition, as the second substance, for example, bis(dialkylamino)dialkoxysilane such as bis(dimethylamino)dimethoxysilane ([(CH3)2N]2Si(OCH3)2) which contains two chemical bonds between the first element and alkoxy groups and two chemical bonds between the first element and amino groups in one molecule can be used.

[0102] In addition, as the second substance, tri(dialkylamino)alkoxysilane such as tri(dimethylamino)methoxysilane ([(CH3)2N]3SiOCH3) which contains one chemical bond between the first element and an alkoxy group and three chemical bonds between the first element and an amino group in one molecule can be used.

[0103] As the second substance, one or more of these can be used. It should be noted that the "1", "2" and "3" mentioned above do not mean the number of the first element but the number of chemical bonds.

[0104] In addition, the controllability of film formation can be improved by using a substance having a higher reactivity (adsorbability) than the first substance as the second substance, that is, using a substance having a lower reactivity (adsorbability) than the second substance as the first substance.

[0105] After the first layer is formed in the concave portion on the surface of the wafer 200, the valve 243b is closed to stop the supply of the second substance to the processing chamber 201. Then, the gaseous substance remaining in the processing chamber 201 is removed (purged) from the processing chamber 201 by the same processing procedure and processing conditions as those in the purge in the first substance supply step. The processing temperature during the purge in this step is preferably set to the same temperature as the processing temperature during the supply of the second substance.

[0106] [Third substance supply step]

[0107] After the second substance supplying step is completed, a third substance containing, for example, oxygen (O) as a second element different from the first element, that is, an oxidant (oxidizing gas), is supplied to the wafer 200 , that is, the wafer 200 after the first layer is formed in the recess.

[0108] Specifically, valve 243c is opened to allow the third substance to flow into the gas supply pipe 232c. The third substance is flow-regulated by MFC241c, supplied to the processing chamber 201 via nozzle 249c, and exhausted by exhaust port 231a. At this time, the third substance is supplied to the wafer 200 from the side of the wafer 200 (third substance supply). At this time, valves 243d to 243f can also be opened to supply inactive gas to the processing chamber 201 via nozzles 249a to 249c, respectively.

[0109] By supplying the third substance to the wafer 200 under the following processing conditions, Figure 5 As shown in (c), at least a portion of the first layer can be oxidized and converted (modified) into a second layer. In this case, the second element is added to the first layer containing the first element, and the second layer becomes a layer containing the first element and the second element, that is, an oxidized layer containing the first element.

[0110] As the processing conditions when supplying the third substance in the third substance supplying step, the following can be exemplified:

[0111] Processing temperature: 400-800°C, preferably 500-800°C

[0112] Processing pressure: 1-4000 Pa, preferably 1-1000 Pa

[0113] Third substance supply flow rate: 0.1 to 10 slm, preferably 1 to 10 slm

[0114] Third substance supply time: 1 to 120 seconds, preferably 1 to 60 seconds

[0115] Inert gas supply flow rate (per gas supply pipe): 0~20slm

[0116] As the third substance (oxidant), for example, an oxygen-containing gas such as oxygen (O 2 ) or water (H 2 O) can be used. As the third substance, one or more of these can be used.

[0117] After the first layer is oxidized and modified into the second layer, the valve 243c is closed to stop the supply of the third substance into the processing chamber 201. Then, the gaseous substance remaining in the processing chamber 201 is removed (purged) from the processing chamber 201 by the same processing procedure and processing conditions as those in the purge in the first substance supply step. The processing temperature during the purge in this step is preferably set to the same temperature as the processing temperature during the supply of the third substance.

[0118] [Scheduled number of implementations]

[0119] By performing the above-mentioned first substance supply step, second substance supply step, and third substance supply step non-simultaneously for n times (n is an integer greater than 1 or 2), a film containing the first element and the second element can be formed in a concave portion on the surface of the wafer 200. As described above, when the first substance and the second substance contain Si as the first element and the third substance contains O as the second element, a silicon oxide film (SiO film) can be formed as a film containing the first element and the second element in the concave portion on the surface of the wafer 200. The above cycle is preferably repeated multiple times. That is, it is preferred that the thickness of the second layer formed in each cycle is thinner than the desired film thickness, and the above cycle is repeated multiple times until the film thickness of the film 600 formed by stacking the second layer reaches the desired film thickness.

[0120] It should be noted that the above-mentioned processing conditions when supplying the third substance in the third substance supplying step are, as described above, processing conditions for forming a film at the first film forming rate when the second substance and the third substance are alternately supplied, and processing conditions for substantially not forming a film when the first substance and the third substance are alternately supplied. That is, the above-mentioned processing conditions are also processing conditions that make the reactivity of the second substance and the third substance extremely high compared to the reactivity of the first substance and the third substance.

[0121] In addition, the above-mentioned processing conditions when supplying the third substance in the third substance supplying step also include the following processing conditions: processing conditions for forming a film of the first thickness in each cycle when the second substance and the third substance are alternately supplied, and processing conditions for making the thickness of the film formed in each cycle (second thickness) substantially zero when the first substance and the third substance are alternately supplied.

[0122] In addition, the above-mentioned processing conditions when supplying the third substance in the third substance supplying step also include the following processing conditions: processing conditions for forming a continuous film when the second substance and the third substance are alternately supplied, and processing conditions for not forming a film when the first substance and the third substance are alternately supplied.

[0123] Thus, during the film forming step, Figure 5As shown in (c), film formation can be effectively suppressed at the upper part of the concave portion of the surface of the wafer 200 and at any place on the surface of the wafer 200 other than the concave portion, and a state where substantially no film is formed can be maintained. Figure 5 As shown in (d), substantially no film is formed on the surface of the wafer 200 except in the recessed portion, and the recessed portion on the surface of the wafer 200 is filled with the film.

[0124] (Post-Purge and Atmospheric Pressure Restoration)

[0125] After the film forming step is completed, an inert gas is supplied from the nozzles 249a to 249c as a purge gas into the processing chamber 201, and the gas is exhausted from the exhaust port 231a. Thus, the processing chamber 201 is purged, and the residual gas, reaction by-products, etc. in the processing chamber 201 are removed from the processing chamber 201 (post-purge). Then, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure recovery).

[0126] (Cassette unloading and wafer release)

[0127] Then, the sealing cap 219 is lowered by the wafer box elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the wafer box 217 (wafer box unloading). After the wafer box is unloaded, the baffle 219s is moved, and the lower end opening of the manifold 209 is sealed by the baffle 219s via the O-ring 220c (closing the baffle). After the processed wafer 200 is carried out to the outside of the reaction tube 203, it is taken out from the wafer box 217 (wafer release).

[0128] (3) Effects of this method

[0129] According to this aspect, one or more of the following effects can be obtained.

[0130] (a) In the film forming step, by performing a cycle including the first substance supply step, the second substance supply step, and the third substance supply step n times on the wafer 200 having the concave portion on the surface, a high-quality, conformal film free of chlorine can be formed in the concave portion with high step coverage. In addition, the concave portion can be filled with no voids and seamlessly with high precision due to the high-quality, chlorine-free film.

[0131] (b) By performing the third substance supply step under the processing conditions of forming a film at the first film forming rate when the second substance and the third substance are alternately supplied, and under the processing conditions of substantially not forming a film when the first substance and the third substance are alternately supplied, film formation on the upper part of the concave portion can be suppressed. As a result, the step coverage of the film formed in the concave portion can be more effectively improved. In addition, the concave portion can be filled with a film without gaps and seamlessly more effectively and with high precision.

[0132] (c) By using the above-mentioned various substances as the first substance and the second substance, during the film forming step, it is possible to more effectively suppress the formation of a film on the upper part of the concave portion on the surface of the wafer 200. As a result, the step coverage of the film formed in the concave portion can be more effectively improved. In addition, the film filling without gaps and seamlessly in the concave portion can be performed more effectively and accurately.

[0133] (d) By using the above-mentioned oxidizing agent as the third substance, a high-quality, conformal oxide film without chlorine can be formed with high step coverage on the concave portion of the surface of the wafer 200. In addition, the high-quality oxide film without chlorine can be used to accurately fill the concave portion without voids and without gaps.

[0134] (e) The above-mentioned effects can also be obtained in the case where a predetermined substance is arbitrarily selected from the above-mentioned various first substances, various second substances, various third substances, and various inert gases for use.

[0135] It should be noted that the step performed under the processing conditions of forming a film at a first film forming rate when the second substance and the third substance are alternately supplied, and the processing conditions of substantially not forming a film when the first substance and the third substance are alternately supplied are not limited to the third substance supply step. In addition, the step performed under the processing conditions of forming a film of the first thickness per cycle when the second substance and the third substance are alternately supplied, and the thickness (second thickness) of the film formed per cycle is substantially zero when the first substance and the third substance are alternately supplied, is not limited to the third substance supply step. In addition, the step performed under the processing conditions of forming a continuous film when the second substance and the third substance are alternately supplied, and the step performed under the processing conditions of not forming a film when the first substance and the third substance are alternately supplied is not limited to the third substance supply step. For example, under such processing conditions, the first substance supply step and the second substance supply step may also be performed. That is, at least any one of the first substance supply step, the second substance supply step, and the third substance supply step may be performed under such processing conditions, and each step, i.e., the film forming step, may also be performed under such processing conditions. It should be noted that the processing conditions exemplified in the above steps include these processing conditions. Even in these cases, the same effects as those described above can be obtained.

[0136] (4) Modification

[0137] The processing sequence in this method can be changed to the following modified examples. These modified examples can be combined arbitrarily. Unless otherwise specified, the processing steps and processing conditions in each step of each modified example can be the same as the processing procedures and processing conditions in each step of the above-mentioned processing sequence.

[0138] (Variant 1)

[0139] The third substance supplying step may be performed under processing conditions in which a film is formed at a first film forming rate when the second substance and the third substance are supplied alternately, and under processing conditions in which a film is formed at a second film forming rate lower than the first film forming rate when the first substance and the third substance are supplied alternately.

[0140] In the first substance supplying step of this modification, the first substance containing no chlorine and containing the first element is supplied to the wafer 200 having the concave portion on the surface by the same processing procedure and processing conditions as those of the first substance supplying step of the above-mentioned embodiment. Figure 6 As shown in (a), X, which is at least a part of the molecular structure of the molecules constituting the first substance, can be adsorbed at the upper portion of the concave portion on the surface of the wafer 200 .

[0141] Furthermore, in the second substance supplying step of this modification, the second substance containing the first element and not containing chlorine is supplied to the wafer 200 after X is adsorbed on the upper part of the concave part of the surface by the same processing procedure and processing conditions as those of the second substance supplying step of the above-mentioned embodiment. Figure 6 As shown in (b), the non-adsorbed portion of X in the concave portion on the surface of the wafer 200 can adsorb Y, which is at least a part of the molecular structure of the molecules constituting the second substance, to form a first layer. The first layer becomes a layer containing the first element. In addition, the non-adsorbed layer of X in the concave portion includes the bottom, lower portion, and central portion in the concave portion.

[0142] It should be noted that in this variation, as the first substance and the second substance, for example, a substance containing a partial structure in which the first element is bonded to an amino group and an alkoxy group, a partial structure in which the first element is bonded to an amino group and an alkyl group, or a partial structure in which the first element is bonded to an amino group and hydrogen can be used. When such substances are used as the first substance and the second substance, X, which is adsorbed on the upper part of the concave portion as at least a part of the molecular structure of the molecule constituting the first substance, may contain at least any one of a chemical bond between the first element and an alkoxy group, a chemical bond between the first element and an alkyl group, a chemical bond between the first element and hydrogen, and a chemical bond between the first element and an amino group. That is, X may contain at least any one of the first element and an alkoxy group, an alkyl group, hydrogen, and an amino group. In addition, Y, which is adsorbed on the non-adsorbed portion of X in the concave portion as at least a part of the molecular structure of the molecule constituting the second substance, may contain at least any one of a chemical bond between the first element and an alkoxy group, a chemical bond between the first element and an alkyl group, a chemical bond between the first element and hydrogen, and a chemical bond between the first element and an amino group. That is, Y may contain at least any one of the first element and an alkoxy group, an alkyl group, hydrogen, and an amino group.

[0143] Here, the number of chemical bonds between the first element and the amino group contained in one molecule of the first substance is preferably greater than the number of chemical bonds between the first element and the amino group contained in one molecule of the second substance. In other words, the number of amino groups contained in one molecule of the first substance is preferably greater than the number of amino groups contained in one molecule of the second substance.

[0144] The first element contains Si, for example. At this time, in this modification, as the first substance, for example, the following substance can be used: containing more than 2 chemical bonds between the first element and amino groups, less than 2 chemical bonds between the first element and alkoxy groups, less than 2 chemical bonds between the first element and alkyl groups, or less than 2 chemical bonds between the first element and hydrogen in one molecule. In addition, in this modification, as the second substance, for example, the following substance can be used: containing 1 chemical bond between the first element and amino groups, 3 chemical bonds between the first element and alkoxy groups, 3 chemical bonds between the first element and alkyl groups, or 3 chemical bonds between the first element and hydrogen in one molecule. The "more than 2", "less than 2", "1", and "3" mentioned here are not the number of the first element, but mean the number of chemical bonds.

[0145] That is, in this variation, as the first substance, for example, bis(dialkylamino)dialkoxysilane such as bis(dimethylamino)dimethoxysilane ([(CH3)2N]2Si(OCH3)2) which contains chemical bonds between two first elements and amino groups, and chemical bonds between two first elements and alkoxy groups in one molecule can be used.

[0146] In addition, in this variation, as the first substance, tri(dialkylamino)alkoxysilane such as tri(dimethylamino)methoxysilane ([(CH3)2N]3SiOCH3) which contains three chemical bonds between the first element and an amino group and one chemical bond between the first element and an alkoxy group in one molecule can be used.

[0147] In addition, in this variation, as the first substance, for example, bis(dialkylamino)dialkylsilane such as bis(dimethylamino)dimethylsilane ([(CH3)2N]2Si(CH3)2) which contains chemical bonds between two first elements and amino groups, and chemical bonds between two first elements and alkyl groups in one molecule can be used.

[0148] In addition, in this variation, as the first substance, tri(dialkylamino)alkylsilane such as tri(dimethylamino)methylsilane ([(CH3)2N]3SiCH3) which contains three chemical bonds between the first element and an amino group and one chemical bond between the first element and an alkyl group in one molecule can be used.

[0149] In addition, in this variation, as the first substance, for example, bis(dialkylamino)silanes such as bis(diethylamino)silane ([(C2H5)2N]2SiH2) and bis(monoalkylamino)silanes such as bis(tert-butylamino)silane ([(C4H9)NH]2SiH2) that contain chemical bonds between two first elements and amino groups and two chemical bonds between the first element and hydrogen in one molecule can be used.

[0150] In addition, in this variation, as the first substance, tri(dialkylamino)silane such as tri(dimethylamino)silane ([(CH3)2N]3SiH) which contains three chemical bonds between the first element and amino groups and one chemical bond between the first element and hydrogen in one molecule can be used.

[0151] In this modification, one or more of these substances may be used as the first substance. It should be noted that "1", "2" and "3" in the above do not refer to the number of the first element but to the number of chemical bonds.

[0152] In addition, in this variation, as the second substance, (dialkylamino)trialkoxysilane such as (dimethylamino)trimethoxysilane ((CH3)2NSi(OCH3)3) which contains one chemical bond between the first element and an amino group and three chemical bonds between the first element and an alkoxy group in one molecule can be used.

[0153] In addition, in this variation, as the second substance, (dialkylamino)trialkylsilane such as (dimethylamino)trimethylsilane ((CH3)2NSi(CH3)3) which contains one chemical bond between the first element and an amino group and three chemical bonds between the first element and an alkyl group in one molecule can be used.

[0154] In addition, in this variation, as the second substance, for example, mono(dialkylamino)silanes such as (diisobutylamino)silane ((C4H9)2NSiH3) and (diisopropylamino)silane ((C3H7)2NSiH3) can be used, which contain one chemical bond between the first element and an amino group and three chemical bonds between the first element and hydrogen in one molecule.

[0155] In this modification, one or more of these substances may be used as the second substance. It should be noted that "1" and "3" in the above do not refer to the number of the first element but to the number of chemical bonds.

[0156] Furthermore, by using a substance having higher reactivity (adsorbability) than the first substance as the second substance, i.e., using a substance having lower reactivity (adsorbability) than the second substance as the first substance, the controllability of film formation can be improved.

[0157] Furthermore, by using a substance having a smaller number of amino groups in one molecule than the first substance as the second substance, the amount of Y adsorbed (adsorption density) in the recess can be made larger (higher) than the amount of X adsorbed (adsorption density) in the recess, and the amount of the first element adsorbed (adsorption density) from the second substance in the recess can be made larger (higher) than the amount of the first element adsorbed (adsorption density) from the first substance in the recess. That is, the amount of the first element adsorbed (adsorption density) in the bottom, lower, and central part of the recess can be made larger (higher) than the amount of the first element adsorbed (adsorption density) in the upper part of the recess. Moreover, this becomes a factor in making the thickness of the layer containing the first element and the second element formed in the bottom, lower, and central part of the recess in each cycle thicker than the thickness of the layer containing the first element and the second element formed in the upper part of the recess in each cycle.

[0158] In the third substance supplying step of this modification, the third substance containing, for example, O as the second element, i.e., an oxidant (oxidizing gas) is supplied to the wafer 200 after the first layer is formed in the concave portion through the same processing procedure as the third substance supplying step of the above-mentioned embodiment. Figure 6 As shown in (c), at least a portion of the first layer can be oxidized and converted (modified) into a second layer. In this case, the second element is added to the first layer containing the first element, and the second layer becomes a layer containing the first element and the second element, that is, an oxidized layer containing the first element.

[0159] When the above-mentioned various substances are used as the first substance and the second substance, in this modification, as the third substance (oxidant), for example, ozone (O3), oxygen (O2) + hydrogen (H2), oxygen (O) radicals, hydroxyl (OH) radicals, etc. O-containing gas (+H-containing gas), O-containing radicals can be used. As the third substance, one or more of these can be used.

[0160] It should be noted that the combined description of two substances such as "O2+H2" in this specification means a mixture of O2 and H2. When supplying the mixture, the two substances can be mixed in the supply pipe (pre-mixed) and then supplied to the processing chamber 201, or the two substances can be supplied to the processing chamber 201 from different supply pipes and then mixed in the processing chamber 201 (post-mixed).

[0161] When at least any one of O2+H2, O radicals, and OH radicals is used as the third substance, the processing conditions when the third substance is supplied in the third substance supplying step may be exemplified as follows:

[0162] Treatment temperature: room temperature (25°C) to 800°C, preferably 200 to 800°C

[0163] Processing pressure: 1-4000 Pa, preferably 1-1000 Pa

[0164] Third substance supply flow rate: 0.01 to 10 slm, preferably 1 to 10 slm

[0165] Third substance supply time: 1 to 120 seconds, preferably 1 to 60 seconds

[0166] Inert gas supply flow rate (per gas supply pipe): 0~20slm

[0167] Furthermore, when at least any one of the above-mentioned bis(dialkylamino)dialkoxysilane and the above-mentioned tri(dialkylamino)alkoxysilane is used as the first substance, and the above-mentioned (dialkylamino)trialkoxysilane is used as the second substance, in this modification, as the third substance (oxidant), in addition to the above-mentioned various substances, an O-containing gas such as O2, H2O, etc. can also be used. As the third substance, one or more of these can be used.

[0168] When at least one of O 2 and H 2 is used as the third substance, the processing conditions when the third substance is supplied in the third substance supplying step can be set to be the same as the processing conditions of the third substance supplying step in the above-mentioned embodiment.

[0169] In this modification, the first substance supply step, the second substance supply step, and the third substance supply step are performed non-simultaneously for n times (n is an integer greater than 1 or 2), as shown in FIG. Figure 6As shown in (d), a film containing the first element and the second element can be formed in the concave portion on the surface of the wafer 200. As described above, when the first substance and the second substance contain Si as the first element and the third substance contains O as the second element, a SiO film can be formed in the concave portion on the surface of the wafer 200.

[0170] It should be noted that the above-mentioned processing conditions when supplying the third substance in the third substance supplying step are, as mentioned above, processing conditions for forming a film at a first film forming rate when the second substance and the third substance are alternately supplied, and processing conditions for forming a film at a second film forming rate lower than the first film forming rate when the first substance and the third substance are alternately supplied.

[0171] Furthermore, the above-mentioned processing conditions when supplying the third substance in the third substance supplying step are processing conditions for forming a film of a first thickness in each cycle when the second substance and the third substance are alternately supplied, and processing conditions for forming a film of a second thickness thinner than the first thickness in each cycle when the first substance and the third substance are alternately supplied. The second thickness is, for example, a thickness of less than one atomic layer.

[0172] In addition, the above-mentioned processing conditions when supplying the third substance in the third substance supply step also include: processing conditions for forming a continuous film when the second substance and the third substance are alternately supplied, and processing conditions for forming a discontinuous island-shaped film when the first substance and the third substance are alternately supplied.

[0173] In addition, the above-mentioned processing conditions when supplying the third substance in the third substance supply step are also processing conditions for forming a continuous film of thickness T1 when the second substance and the third substance are alternately supplied a predetermined number of times, and processing conditions for forming a film of thickness T2 thinner than thickness T1 when the first substance and the third substance are alternately supplied a predetermined number of times.

[0174] Thus, during the film forming step, Figure 6 As shown in (c), at the upper part of the concave portion of the surface of the wafer 200 and at any place on the surface of the wafer 200 except the concave portion, when the cycle is performed, a layer (film) containing the first element and the second element is formed with a thickness thinner than the layer (film) containing the first element and the second element formed at the bottom, lower part, and central part of the concave portion. In addition, when the film forming step is further continued, as shown in Figure 6 As shown in (d), the concave portion on the surface of the wafer 200 is filled with the film, and a film having a predetermined thickness is also formed on the surface of the wafer 200 except in the concave portion.

[0175] In this modification, substantially the same effects as those in the above-described embodiment can be obtained.

[0176] That is, a high-quality, conformal film containing no chlorine can be formed with high step coverage in the recessed portion on the surface of the wafer 200. In addition, the recessed portion can be filled with no voids and without gaps with high accuracy using the high-quality, chlorine-free film.

[0177] In addition, by performing the third substance supply step under processing conditions in which a film is formed at a first film forming rate when the second substance and the third substance are alternately supplied, and under processing conditions in which a film is formed at a second film forming rate lower than the above-mentioned first film forming rate when the first substance and the third substance are alternately supplied, the formation of a film on the upper portion of the recess on the surface of the wafer 200 can be suppressed, and at the same time, a film of appropriate thickness can be formed on the upper portion of the recess, thereby improving the yield of substrate processing, that is, the productivity of substrate processing.

[0178] In addition, by using the above-mentioned various substances as the first substance and the second substance, the formation of a film on the upper part of the recessed portion on the surface of the wafer 200 can be suppressed, and at the same time, a film of appropriate thickness can be effectively formed on the upper part of the recessed portion, thereby more effectively improving the yield of substrate processing, that is, the productivity of substrate processing.

[0179] Furthermore, by using the above oxidizing agent as the third substance, a high-quality, conformal oxide film without chlorine can be formed with high step coverage on the concave portion of the surface of the wafer 200. Furthermore, the high-quality oxide film without chlorine can be accurately filled without voids and without gaps.

[0180] The above-mentioned effects can also be obtained in the case of arbitrarily selecting and using a predetermined substance from among the various first substances, various second substances, various third substances, and various inert gases.

[0181] It should be noted that the step performed under the processing conditions of forming a film at a first film forming rate when the second substance and the third substance are alternately supplied, and the step performed under the processing conditions of forming a film at a second film forming rate lower than the first film forming rate when the first substance and the third substance are alternately supplied is not limited to the third substance supplying step. In addition, the step performed under the processing conditions of forming a film of a first thickness in each cycle when the second substance and the third substance are alternately supplied, and the step performed under the processing conditions of forming a film of a second thickness thinner than the first thickness in each cycle when the first substance and the third substance are alternately supplied is not limited to the third substance supplying step. In addition, the step performed under the processing conditions of forming a continuous film when the second substance and the third substance are alternately supplied, and the step performed under the processing conditions of forming a discontinuous island film when the first substance and the third substance are alternately supplied is not limited to the third substance supplying step. In addition, the step performed under the processing conditions of forming a continuous film of thickness T1 when the second substance and the third substance are alternately supplied a predetermined number of times, and the step performed under the processing conditions of forming a film of thickness T2 thinner than thickness T1 when the first substance and the third substance are alternately supplied a predetermined number of times is not limited to the third substance supplying step. For example, under such processing conditions, the first substance supply step and the second substance supply step may be performed. It should be noted that, as described above, the situation in which a substance having fewer amino groups contained in one molecule than the first substance is used as the second substance, that is, the situation in which a substance having more amino groups contained in one molecule than the second substance is used as the first substance, is also included in such processing conditions. That is, at least any one of the first substance supply step, the second substance supply step, and the third substance supply step may be performed under such processing conditions, and each step, that is, the film forming step, may also be performed under such processing conditions. It should be noted that the processing conditions exemplified in the above steps also include these processing conditions. Even in these cases, the same effect as the above effect can be obtained.

[0182] (Variant 2)

[0183] As shown in the processing order below, the film forming step may also include: performing a first substance supply step, and alternating the second substance supply step and the third substance supply step m times (m is an integer greater than 1 or 2) in a cycle n times (n is an integer greater than 1 or 2).

[0184] [first substance→(second substance→third substance)×m]×n

[0185] In this modification, the same effects as those of the above embodiment can be obtained. In addition, according to this modification, the controllability of the composition ratio of the film formed in the concave portion can be improved.

[0186] It should be noted that in this modification, in addition to increasing the number of cycles, the value of m can also be changed. For example, the value of m can be set to be relatively small in the initial stage of the film forming step, and the value of m can be gradually increased as the film filling process in the concave portion proceeds. In this way, it is possible to suppress the gradual decrease in productivity as the film filling process in the concave portion proceeds.

[0187] (Variant 3)

[0188] When the cycle of the non-simultaneous first substance supplying step, second substance supplying step, and third substance supplying step is performed a predetermined number of times, in addition to increasing the number of cycles, the processing conditions for supplying the first substance in the first substance supplying step may be changed.

[0189] For example, in the initial stage of the film forming step, the first substance supply time in the first substance supply step may be set to be relatively long, and the value (supply time) may be gradually reduced as the film filling process in the recess proceeds. Also, for example, in the initial stage of the film forming step, the first substance supply flow rate in the first substance supply step may be set to be relatively large, and the value (supply flow rate) may be gradually reduced as the film filling process in the recess proceeds. Also, for example, in the initial stage of the film forming step, the processing pressure when supplying the first substance in the first substance supply step may be set to be relatively high, and the value (processing pressure) may be gradually reduced as the film filling process in the recess proceeds. Also, for example, in the initial stage of the film forming step, the partial pressure of the first substance in the processing chamber 201 when supplying the first substance in the first substance supply step may be set to be relatively high, and the value (partial pressure) may be gradually reduced as the film filling process in the recess proceeds.

[0190] In this modification, the same effects as those in the above embodiment can be obtained. In addition, according to this modification, it is possible to suppress a gradual decrease in productivity as the film filling process in the recessed portion proceeds.

[0191] (Variant 4)

[0192] like Figure 5As shown in (d), on the surface of the wafer 200 after the film forming step is implemented, there is a situation where X, which is at least a part of the molecular structure of the molecules constituting the first substance, remains in an adsorbed state. In addition, X also remains at the interface between the film and the recess, and there is also a situation where it remains in the film. Here, it is also possible to supply a modifier to the wafer 200 after the film forming step, as in the processing sequence shown below, and further perform a step (modification step) of modifying the film formed in the recess and the surface of the wafer 200 (n, m are integers greater than 1 or 2). As a modifier, O3, O2+H2, O radicals, OH radicals, etc., which are exemplified by the third substance, can be used, for example, O-containing gases (+H-containing gases), O-containing radicals.

[0193] (first substance → second substance → third substance) × n → modifier

[0194] [First substance → (Second substance → Third substance) × m] × n → Modifier

[0195] The processing procedure of the modification step can be the same as the processing procedure of the third substance supplying step in the above-mentioned embodiment.

[0196] As the treatment conditions when supplying the modifying agent in the modifying step, the following can be exemplified:

[0197] Treatment temperature: room temperature (25°C) to 1000°C, preferably 200 to 800°C

[0198] Processing pressure: 1-4000 Pa, preferably 1-1000 Pa

[0199] Modifier supply flow rate: 0.01 to 10 slm, preferably 1 to 10 slm

[0200] Modifier supply time: 1 to 18,000 seconds, preferably 120 to 10,800 seconds

[0201] Inert gas supply flow rate (per gas supply pipe): 0~20slm

[0202] In this modification, the same effect as in the above-mentioned method can be obtained. In addition, according to this modification, by performing the modification step, X remaining at the interface between the film and the concave portion can be removed from the interface. In addition, X remaining in the film can be removed from the film. As a result, the film quality of the film formed in the concave portion can be improved. In addition, as Figure 5 As shown in (e), X adsorbed on the surface of the wafer 200 can also be removed from the surface of the wafer 200.

[0203] It should be noted that the modification step may be performed not only at the end of film formation but also at any time during film formation as shown below (n, m, and p are each an integer of 1 or 2 or more).

[0204] [(first substance→second substance→third substance)×n→modification]×p

[0205] {[first substance → (second substance → third substance) × m] × n → modification} × p

[0206] Even in these cases, the same effects as those of the above method can be obtained. In addition, by performing the modification step at the end of film formation or at any time during film formation, the film quality of the film formed in the concave portion can be further improved. Figure 5 As shown in (e), X adsorbed on the surface of the wafer 200 can also be removed from the surface of the wafer 200.

[0207] It should be noted that the film forming step and the modification step are preferably performed in the same processing chamber (in-situ), so that the wafer 200 is not exposed to the atmosphere, that is, the film forming step and the modification step are performed while the surface of the wafer 200 is kept clean.

[0208] <Other aspects of the present disclosure>

[0209] The embodiments of the present disclosure have been specifically described above. However, the present disclosure is not limited to the above embodiments, and various modifications can be made without departing from the gist of the present disclosure.

[0210] For example, the present disclosure can be suitably applied to the case where an oxide film containing a semiconductor element such as a silicon oxynitride film (SiON film), a silicon oxycarbonitride film (SiOCN film), or a silicon oxycarbide film (SiOC film), or an oxide film containing a metal element such as a hafnium oxide film (HfO film), a zirconium oxide film (ZrO film), or an aluminum oxide film (AlO film) is formed in a concave portion on the surface of a substrate in addition to a SiO film. This method can also achieve the same effects as the above method.

[0211] The recipes used in each treatment are preferably prepared separately according to the treatment content, and are pre-recorded and stored in the storage device 121c via the communication circuit and the external storage device 123. Moreover, it is preferred that when each treatment is started, the CPU 121a appropriately selects a suitable recipe from the multiple recipes recorded and stored in the storage device 121c according to the treatment content. Thus, films of various film types, composition ratios, film qualities, and film thicknesses can be formed with good reproducibility in the treatment device. In addition, the burden on the operator can be reduced, and various treatments can be started quickly by avoiding operational errors.

[0212] The above recipe is not limited to the case of newly making, for example, it can be prepared by changing an existing recipe already installed in a processing device. When changing the process recipe, the changed recipe can be installed in the substrate processing device via a communication circuit and a recording medium recording the recipe. In addition, the input and output device 122 of the existing processing device can be operated to directly change the existing recipe already installed in the processing device.

[0213] In the above-mentioned method, an example of forming a film using a batch-type substrate processing device that processes multiple substrates at a time is described. The present disclosure is not limited to the above-mentioned method, and for example, it can also be appropriately applied when a film is formed using a single-wafer processing device that processes one or more substrates at a time. In addition, in the above-mentioned method, an example of forming a film using a processing device having a hot-wall type processing furnace is described. The present disclosure is not limited to the above-mentioned method, and it can also be appropriately applied when a film is formed using a processing device having a cold-wall type processing furnace.

[0214] In addition, in the above-mentioned method, an example of performing the above-mentioned processing sequence in the same processing chamber (in-situ) of the same processing device is described. The present disclosure is not limited to the above-mentioned method, for example, any step of the above-mentioned processing sequence and any other step may be performed in different processing chambers (ex-situ) of different processing devices, or may be performed in different processing chambers of the same processing device.

[0215] When these substrate processing apparatuses are used, each process can be performed according to the same processing procedures and processing conditions as those of the above-mentioned embodiments and modified examples, and the same effects as those of the above-mentioned embodiments and modified examples can be obtained.

[0216] The above-mentioned aspects and modifications may be used in combination as appropriate. The processing procedures and processing conditions in this case may be the same as those of the above-mentioned aspects and modifications, for example.

[0217] Explanation of symbols

[0218] 200 wafers (substrates)

Claims

1. A processing method comprising the step of forming a film containing a first element and a second element in a concave portion by performing a cycle comprising the following (a), (b) and (c) n times, wherein: n is an integer of 1 or more than 2, (a) supplying a first substance containing the first element and not containing chlorine to a substrate having a concave portion on its surface, thereby adsorbing at least a portion X of a molecular structure of molecules constituting the first substance at an upper portion of the concave portion; (b) supplying a second substance containing the first element and not containing chlorine to the substrate, so that at least a part Y constituting a molecular structure of molecules of the second substance is adsorbed on the non-adsorbed portion of X in the concave portion to form a first layer; (c) supplying a third substance containing a second element different from the first element to the substrate to modify the first layer into a second layer, (c) is performed under processing conditions in which the film is formed at a first film forming rate when the second substance and the third substance are alternately supplied, and under processing conditions in which the film is formed at a second film forming rate lower than the first film forming rate when the first substance and the third substance are alternately supplied; or (c) is performed under processing conditions in which the film is formed at a first film forming rate when the second substance and the third substance are alternately supplied, and under processing conditions in which the film is not substantially formed when the first substance and the third substance are alternately supplied.

2. The processing method according to claim 1, wherein: (c) is performed under processing conditions in which the film of the first thickness is formed in each cycle when the second substance and the third substance are alternately supplied, and under processing conditions in which the film of the second thickness thinner than the first thickness is formed in each cycle when the first substance and the third substance are alternately supplied.

3. The processing method according to claim 2, wherein: The second thickness is substantially zero.

4. The processing method according to claim 2, wherein: The second thickness is less than one atomic layer.

5. The processing method according to claim 1, wherein: (c) is carried out under processing conditions where the second substance and the third substance are alternately supplied to form a continuous film, and under processing conditions where the first substance and the third substance are alternately supplied to form a discontinuous island film; or (c) is carried out under processing conditions where the second substance and the third substance are alternately supplied to form a continuous film, and under processing conditions where the first substance and the third substance are alternately supplied to form no film.

6. The processing method according to claim 1, wherein: (c) is performed under processing conditions in which the second substance and the third substance are alternately supplied a predetermined number of times to form a continuous film of thickness T1, and under processing conditions in which the first substance and the third substance are alternately supplied the predetermined number of times to form a film of thickness T2 thinner than thickness T1.

7. The processing method according to claim 1, wherein: The cycle comprises: performing (a); and performing (b) and (c) alternately m times, where m is an integer greater than 1 or 2.

8. The processing method according to any one of claims 1 to 7, wherein: The first substance includes a partial structure in which the first element is bonded to an amino group and an alkyl group, or a partial structure in which the first element is bonded to an amino group and hydrogen, and the second substance includes a partial structure in which the first element is bonded to an amino group and an alkoxy group.

9. The processing method according to any one of claims 1 to 7, wherein: The first substance contains one or more chemical bonds between the first element and an alkyl group, and three or less chemical bonds between the first element and an amino group in one molecule; or contains one or more chemical bonds between the first element and hydrogen, and three or less chemical bonds between the first element and an amino group in one molecule; The second substance contains one or more chemical bonds between the first element and an alkoxy group, and three or less chemical bonds between the first element and an amino group in one molecule.

10. The processing method according to any one of claims 1 to 7, wherein: The first substance contains at least any one of (dialkylamino)trialkylsilane, bis(dialkylamino)dialkylsilane, tri(dialkylamino)alkylsilane, mono(dialkylamino)silane, bis(dialkylamino)silane, and tri(dialkylamino)silane; The second substance contains at least any one of (dialkylamino)trialkoxysilane, bis(dialkylamino)dialkoxysilane, and tris(dialkylamino)alkoxysilane.

11. The processing method according to any one of claims 1 to 7, wherein: The first substance and the second substance include a partial structure in which the first element is bonded to an amino group and an alkoxy group, a partial structure in which the first element is bonded to an amino group and an alkyl group, or a partial structure in which the first element is bonded to an amino group and hydrogen.

12. The processing method according to claim 11, wherein: The number of chemical bonds between the first element and the amino group contained in one molecule of the first substance is greater than the number of chemical bonds between the first element and the amino group contained in one molecule of the second substance.

13. The processing method according to any one of claims 1 to 7, wherein: The first substance contains in one molecule: Two or more chemical bonds between the first element and an amino group; and No more than two chemical bonds between the first element and an alkoxy group, no more than two chemical bonds between the first element and an alkyl group, or no more than two chemical bonds between the first element and hydrogen; The second substance contains in one molecule: 1 chemical bond between the first element and an amino group; and three chemical bonds between the first element and an alkoxy group, three chemical bonds between the first element and an alkyl group, or three chemical bonds between the first element and hydrogen.

14. The processing method according to any one of claims 1 to 7, wherein: The first substance contains at least one of bis(dialkylamino)dialkoxysilane, tri(dialkylamino)alkoxysilane, bis(dialkylamino)dialkylsilane, tri(dialkylamino)alkylsilane, bis(dialkylamino)silane, and tri(dialkylamino)silane; The second substance contains at least any one of (dialkylamino)trialkoxysilane, (dialkylamino)trialkylsilane, and mono(dialkylamino)silane.

15. The processing method according to any one of claims 1 to 7, wherein: The third substance is an oxidant.

16. The processing method according to claim 10, wherein: The third substance contains at least any one of O 2 and H 2 O.

17. The processing method according to claim 14, wherein: The third substance contains at least any one of O 3 , O 2 + H 2 , O radicals, and OH radicals.

18. The processing method according to any one of claims 1 to 7, wherein: The first substance contains at least one of bis(dialkylamino)dialkoxysilane and tris(dialkylamino)alkoxysilane; The second substance contains (dialkylamino)trialkylsilane; The third substance contains at least any one of O 2 and H 2 O.

19. A method for manufacturing a semiconductor device, comprising the step of forming a film containing a first element and a second element in a concave portion by performing a cycle comprising the following (a), (b) and (c) n times, wherein: n is an integer of 1 or more than 2, (a) supplying a first substance containing a first element and not containing chlorine to a substrate having a concave portion on its surface, and causing at least a portion X of a molecular structure constituting a molecule of the first substance to be adsorbed at an upper portion of the concave portion; (b) supplying a second substance containing the first element and not containing chlorine to the substrate, so that at least a part Y constituting the molecular structure of molecules of the second substance is adsorbed on the non-adsorbed portion of X in the recessed portion to form a first layer; and (c) supplying a third substance containing a second element different from the first element to the substrate to modify the first layer into a second layer, (c) is performed under processing conditions in which the film is formed at a first film forming rate when the second substance and the third substance are alternately supplied, and under processing conditions in which the film is formed at a second film forming rate lower than the first film forming rate when the first substance and the third substance are alternately supplied; or (c) is performed under processing conditions in which the film is formed at a first film forming rate when the second substance and the third substance are alternately supplied, and under processing conditions in which the film is not substantially formed when the first substance and the third substance are alternately supplied.

20. A processing device comprising: A first substance supply system supplies a first substance containing a first element and not containing chlorine to the substrate; a second substance supply system for supplying a second substance containing the first element and not containing chlorine to the substrate; a third substance supply system for supplying a third substance containing a second element different from the first element to the substrate; a heater for heating the substrate; and A control unit configured to control the first substance supply system, the second substance supply system, the third substance supply system, and the heater so that a process is performed to form a film containing the first element and the second element in the concave portion by performing a cycle including the following (a), (b), and (c) n times, wherein: n is an integer of 1 or 2 or more: (a) a process of supplying the first substance to a substrate having a concave portion on its surface to adsorb at least a portion X of the molecular structure of the molecules constituting the first substance in the upper portion of the concave portion; (b) a process of supplying the second substance to the substrate to adsorb at least a portion Y of the molecular structure of the molecules constituting the second substance in the non-adsorbed portion of X in the concave portion to form a first layer; (c) a process of supplying the third substance to the substrate to modify the first layer into a second layer, the process (c) being performed under the process conditions that the film is formed at a first film forming rate when the second substance and the third substance are alternately supplied, and under the process conditions that the film is formed at a second film forming rate lower than the first film forming rate when the first substance and the third substance are alternately supplied; or (c) being performed under the process conditions that the film is formed at a first film forming rate when the second substance and the third substance are alternately supplied, and under the process conditions that the film is substantially not formed when the first substance and the third substance are alternately supplied.

21. A program that causes a processing device to execute the following process via a computer: A process for forming a film containing a first element and a second element in a concave portion by performing a cycle comprising the following (a), (b) and (c) n times, wherein: n is an integer greater than 1 or 2: (a) a process of supplying a first substance containing a first element and not containing chlorine to a substrate having a concave portion on its surface, and adsorbing at least a portion X of a molecular structure of a molecule constituting the first substance at an upper portion of the concave portion; (b) a process of forming a first layer by supplying a second substance containing the first element and not containing chlorine to the substrate, so that at least a part Y constituting the molecular structure of the molecules of the second substance is adsorbed on the non-adsorbed portion of X in the concave portion; (c) supplying a third substance containing a second element different from the first element to the substrate to modify the first layer into the second layer; as well as Process (c) is performed under processing conditions in which the film is formed at a first film forming rate when the second substance and the third substance are alternately supplied, and under processing conditions in which the film is formed at a second film forming rate lower than the first film forming rate when the first substance and the third substance are alternately supplied; or process (c) is performed under processing conditions in which the film is formed at a first film forming rate when the second substance and the third substance are alternately supplied, and under processing conditions in which the film is not substantially formed when the first substance and the third substance are alternately supplied.

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