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

Abstract

The present invention includes: (a) a step for supplying, under a first temperature, a first reactant to a substrate having a surface in which a recess is formed to expose an oxygen-containing film and thereby forming a non-fluid film on the surface of the substrate; and (b) a step for supplying a second reactant to the substrate under a second temperature lower than the first temperature and thereby forming a fluid film over the non-fluid film.

Description

[Technical Field]

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

[0002] As one step in the manufacturing process of a semiconductor device, a process of forming a film on a substrate may be performed (see, for example, Patent Documents 1 and 2). In this case, a process of forming a fluid film (hereinafter also referred to as a fluid film) on a substrate having a recessed portion on its surface may be performed. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-34196 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-30752 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure aims to improve the properties of a film formed on a substrate having a recessed portion formed on its surface. [Means for solving the problem]

[0005] According to one aspect of the present disclosure, (a) forming a non-flowable film on a surface of a substrate having a recessed portion and an exposed oxygen-containing film by supplying a first reactant at a first temperature to the surface of the substrate; (b) providing a second reactant to the substrate at a second temperature lower than the first temperature to form a flowable film on the non-flowable film; Techniques for doing this are provided. [Effects of the Invention]

[0006] According to the present disclosure, it is possible to improve the properties of a film formed on a substrate having a recessed portion on its surface. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic diagram of a vertical processing furnace of a substrate processing apparatus suitably used in each aspect of the present disclosure, showing a vertical cross-sectional view of the processing furnace portion. [Figure 2] FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus that can be suitably used in each aspect of the present disclosure, and is a cross-sectional view of the processing furnace portion taken along line AA in FIG. [Figure 3] FIG. 3 is a schematic configuration diagram of a controller of a substrate processing apparatus preferably used in each aspect of the present disclosure, and is a block diagram showing a control system of the controller. [Figure 4] FIG. 4 is a diagram showing a substrate processing sequence according to the first embodiment of the present disclosure. [Figure 5] FIG. 5 is a diagram showing a substrate processing sequence according to the second embodiment of the present disclosure. [Figure 6] FIG. 6 is a diagram showing a substrate processing sequence according to the third aspect of the present disclosure. [Figure 7] FIG. 7 shows examples and comparative examples. [Figure 8] FIG. 8(a) is a partial enlarged cross-sectional view of the wafer surface in the example, and FIG. 8(b) is a partial enlarged cross-sectional view of the wafer surface in the comparative example. DETAILED DESCRIPTION OF THE INVENTION

[0008] <First Aspect of the Present Disclosure> The first embodiment of the present disclosure will be described below mainly with reference to Figures 1 to 4. Note that the drawings used in the following description are all schematic, and the dimensional relationships between elements, the ratios of elements, etc. shown in the drawings do not necessarily match those in reality. Furthermore, the dimensional relationships between elements, the ratios of elements, etc. do not necessarily match between multiple drawings.

[0009] (1) Configuration of the substrate processing equipment 1, the process furnace 202 has a heater 207 as a heating mechanism (temperature adjustment unit). The heater 207 is cylindrical and is installed vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gases with heat.

[0010] A reaction tube 203 is disposed concentrically with the heater 207 inside the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and has a cylindrical shape with a closed upper end and an open lower end. A manifold 209 is disposed concentrically with the reaction tube 203 below the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS) and has a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing member. The reaction tube 203 is installed vertically, similar to the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in the cylindrical hollow portion of the processing vessel. The processing chamber 201 is configured to be able to accommodate wafers 200 as substrates. In the processing chamber 201, processing of the wafers 200 is performed.

[0011] Nozzles 249a to 249c serving as first to third supply units are provided within the processing chamber 201 so as to penetrate the sidewall of the manifold 209, respectively. The nozzles 249a to 249c are also referred to as first to third nozzles. The nozzles 249a to 249c are made of a heat-resistant non-metallic material such as quartz or SiC. Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively. The nozzles 249a to 249c are different nozzles, and each of the nozzles 249a and 249c is provided adjacent to the nozzle 249b.

[0012] Gas supply pipes 232a to 232c are respectively provided with mass flow controllers (MFCs) 241a to 241c, which are flow rate control devices (flow rate control parts), and valves 243a to 243c, which are on-off valves, in order from the upstream side of the gas flow. Gas supply pipe 232e is connected to gas supply pipe 232a downstream of valve 243a. Gas supply pipes 232d and 232f are connected to gas supply pipe 232b downstream of valve 243b. Gas supply pipe 232g is connected to gas supply pipe 232c downstream of valve 243c. Gas supply pipes 232d to 232g are respectively provided with MFCs 241d to 241g and valves 243d to 243g in order from the upstream side of the gas flow. Gas supply pipes 232a to 232g are made of a metal material, such as SUS.

[0013] As shown in FIG. 2, the nozzles 249a to 249c are respectively provided in an annular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, extending from the lower part to the upper part of the inner wall of the reaction tube 203 and rising upward in the arrangement direction of the wafers 200. That is, the nozzles 249a to 249c are respectively provided in regions horizontally surrounding the wafer arrangement region on the sides of the wafer arrangement region where the wafers 200 are arranged, and extending along the wafer arrangement region. In a plan view, the nozzle 249b is disposed so as to face an exhaust port 231a (described later) on a straight line across the center of the wafer 200 loaded into the processing chamber 201. The nozzles 249a and 249c are disposed so as to sandwich a line L passing through the nozzle 249b and the center of the exhaust port 231a along the inner wall of the reaction tube 203 (the outer periphery of the wafers 200) from both sides. The line L also passes through the nozzle 249b and the center of the wafer 200. In other words, the nozzle 249c is provided on the opposite side of the line L from the nozzle 249a. The nozzles 249a and 249c are arranged symmetrically, that is, symmetrically, with the line L as the axis of symmetry. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. Each of the gas supply holes 250a to 250c opens to face (face) the exhaust port 231a in a plan view, and is able to supply gas toward the wafers 200. A plurality of the gas supply holes 250a to 250c are provided from the bottom to the top of the reaction tube 203.

[0014] A first source as a first reactant and a second source as a second reactant are supplied from the gas supply pipe 232a into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.

[0015] A first reactant is supplied from the gas supply pipe 232b into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.

[0016] A second reactant as a second reactant is supplied from the gas supply pipe 232c into the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c.

[0017] A third reactant as a second reactant is supplied from the gas supply pipe 232d into the processing chamber 201 via the MFC 241d, the valve 243d, the gas supply pipe 232b, and the nozzle 249b.

[0018] Inert gases are supplied from the gas supply pipes 232e to 232g through the MFCs 241e to 241g, the valves 243e to 243g, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c into the processing chamber 201. The inert gases act as purge gases, carrier gases, dilution gases, etc.

[0019] A first reactant supply system (first raw material supply system, first reactant supply system) is mainly constituted by gas supply pipes 232a, 232b, MFCs 241a, 241b, and valves 243a, 243b. A second reactant supply system (second raw material supply system, second reactant supply system, third reactant supply system) is mainly constituted by gas supply pipes 232a, 232c, and 232d, MFCs 241a, 241c, and 241d, and valves 243a, 243c, and 243d. An inert gas supply system is mainly constituted by gas supply pipes 232e to 232g, MFCs 241e to 241g, and valves 243e to 243g.

[0020] Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which valves 243a-243g, MFCs 241a-241g, etc. are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a-232g, and is configured so that the supply operation of various gases into the gas supply pipes 232a-232g, i.e., the opening and closing operation of the valves 243a-243g and the flow rate adjustment operation by the MFCs 241a-241g, etc., are controlled by a controller 121, which will be described later. The integrated supply system 248 is configured as an integrated or separate integrated unit, and can be attached and detached to and from the gas supply pipes 232a-232g, etc., so that maintenance, replacement, expansion, etc. of the integrated supply system 248 can be performed on an integrated unit basis.

[0021] An exhaust port 231a for exhausting the atmosphere inside the processing chamber 201 is provided at the bottom of the sidewall of the reaction tube 203. As shown in FIG. 2, the exhaust port 231a is provided at a position facing (opposite) the nozzles 249a-249c (gas supply holes 250a-250c) across the wafer 200 in a plan view. The exhaust port 231a may be provided along the sidewall of the reaction tube 203 from the bottom to the top, i.e., along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. The exhaust pipe 231 is made of a metal material such as SUS. A vacuum pump 246 serving as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 serving as a pressure detector (pressure detection unit) for detecting the pressure inside the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 serving as a pressure regulator (pressure adjustment unit). The APC valve 244 is configured to be able to evacuate and stop the evacuation of the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating, and further, to be able to adjust the pressure inside the processing chamber 201 by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating. An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may be considered to be included in the exhaust system.

[0022] A seal cap 219 serving as a furnace port cover capable of airtightly closing the lower end opening of the manifold 209 is provided below the manifold 209. The seal cap 219 is made of a metal material such as SUS and is formed in a disk shape. An O-ring 220b serving as a sealing member that abuts against the lower end of the manifold 209 is provided on the upper surface of the seal cap 219. A rotation mechanism 267 for rotating the boat 217 (described later) is provided below the seal cap 219. A rotation shaft 255 of the rotation mechanism 267 is made of a metal material such as SUS and is connected to the boat 217 through the seal cap 219. The rotation mechanism 267 is configured to rotate the boat 217, thereby rotating the wafers 200. The seal cap 219 is configured to be vertically raised and lowered by a boat elevator 115 serving as a lifting mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers the wafers 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219.

[0023] A shutter 219s is provided below the manifold 209 as a furnace port cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is removed from the processing chamber 201. The shutter 219s is made of a metal material such as SUS and has a disk shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that abuts against the lower end of the manifold 209. The opening and closing operation (lifting and lowering operation, rotating operation, etc.) of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

[0024] The boat 217 as a substrate support is configured to support a plurality of wafers 200, for example, 25 to 200 wafers 200, in a horizontal position and aligned vertically with their centers aligned, i.e., arranged at intervals, in multiple stages. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, heat insulating plates 218, also made of a heat-resistant material such as quartz or SiC, are supported in multiple stages.

[0025] A temperature sensor 263 serving as a temperature detector is installed inside the reaction tube 203. By adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 can be adjusted to a desired temperature distribution. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0026] 3, the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122 configured as, for example, a touch panel is connected to the controller 121. An external storage device 123 can also be connected to the controller 121.

[0027] The storage device 121c is configured with, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. Control programs for controlling the operation of the substrate processing apparatus, process recipes describing procedures and conditions for substrate processing (described later), etc., are readably stored in the storage device 121c. The process recipe is a combination of procedures for substrate processing (described later) that are executed by the controller 121 in the substrate processing apparatus to obtain a predetermined result, and functions as a program. Hereinafter, the process recipes, control programs, etc. are collectively referred to simply as programs. The process recipes are also simply referred to as recipes. In this specification, the term "program" may refer to a recipe alone, a control program alone, or both. The RAM 121b is configured as a memory area (work area) for temporarily storing programs, data, etc. read by the CPU 121a.

[0028] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241g, valves 243a to 243g, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, shutter opening / closing mechanism 115s, and the like.

[0029] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to an input of an operation command from the input / output device 122. The CPU 121a is configured to control, in accordance with the contents of the read recipe, the flow rate adjustment operation of various gases by the MFCs 241a to 241g, the opening and closing operations of the valves 243a to 243g, the opening and closing operation of the APC valve 244 and the pressure adjustment operation by the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, and the like.

[0030] The controller 121 can be configured by installing the above-mentioned program stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, a USB memory, a semiconductor memory such as an SSD, etc. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to simply as recording media. When the term recording media is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both. Note that the program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0031] (2) Substrate processing process An example of a processing sequence for forming a film on the surface of a wafer 200 as a substrate using the above-mentioned substrate processing apparatus as one step in a semiconductor device manufacturing process will be described mainly with reference to FIG. In this embodiment, an example will be described in which the wafer 200 is a silicon substrate (silicon wafer) having recesses such as trenches and holes formed on its surface and exposing an O-containing film such as a silicon (Si) and oxygen (O)-containing film. The O-containing film exposed on the surface of the wafer 200 may be a native oxide film. In the following description, the operation of each component of the substrate processing apparatus is controlled by a controller 121.

[0032] As shown in FIG. 4, in the processing sequence of this embodiment, a step A (non-fluidic film formation) of supplying a first reactant (first source material, first reactant) at a first temperature to a wafer 200 having a recess formed on its surface and an exposed O-containing film, thereby forming a non-fluidic film on the surface of the wafer 200; Step B (fluid film formation) is performed in which a second reactant (second raw material, second reactant, third reactant) is supplied to the wafer 200 at a second temperature lower than the first temperature to form a fluid film on the non-fluid film.

[0033] 4 shows an example in which the first raw material and the second raw material are the same raw material, and the first reactant and the third reactant are the same reactant. That is, FIG. 4 shows an example in which the molecular structures of the first raw material and the second raw material are the same, and the molecular structures of the first reactant and the third reactant are the same. This also applies to FIGS. 5 and 6 in the second and third embodiments described later.

[0034] In addition, in the processing sequence of this embodiment, After the flowable film is formed on the non-flowable film, the wafer 200 is subjected to a post-treatment at a third temperature higher than the second temperature, thereby modifying the flowable film (Step C (post-treatment)). In this specification, the post-treatment is also referred to as PT).

[0035] In the processing sequence of this embodiment, In the above-described step A, a cycle including step A1 of supplying a first raw material to the wafer 200 and step A2 of supplying a first reactant to the wafer 200 is performed a predetermined number of times (m times, where m is an integer equal to or greater than 1). In the processing sequence of this embodiment, steps A1 and A2 are performed non-simultaneously.

[0036] In addition, in the processing sequence of this embodiment, In the above-mentioned step B, a cycle including step B1 of supplying a second raw material to wafer 200, step B2 of supplying a second reactant to wafer 200, and step B3 of supplying a third reactant to wafer 200 is performed a predetermined number of times (n times, n is an integer equal to or greater than 1). In the processing sequence of this embodiment, steps B1, B2, and B3 are performed non-simultaneously.

[0037] In this specification, the above-described processing sequence may be expressed as follows for convenience: Similar notations will be used in the following explanations of modified examples including the second and third aspects.

[0038] (First raw material → First reactant) × m → (Second raw material → Second reactant → Third reactant) × n → PT

[0039] In this specification, the term "wafer" may refer to the wafer itself or a laminate of the wafer and a predetermined layer or film formed on its surface. In this specification, the term "surface of a wafer" may refer to the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. In this specification, the phrase "forming a predetermined layer on a wafer" may mean forming a predetermined layer directly on the surface of the wafer itself or forming a predetermined layer on a layer or the like formed on the wafer. In this specification, the term "substrate" is also synonymous with the term "wafer".

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

[0041] (pressure and temperature regulation) After the boat loading is completed, the processing chamber 201, i.e., the space in which the wafers 200 are present, is evacuated (reduced pressure exhausted) by the vacuum pump 246 so that the interior of the processing chamber 201 is at a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information (pressure adjustment). Furthermore, the wafers 200 inside the processing chamber 201 are heated by the heater 207 so that the temperature is maintained at a desired processing temperature. At this time, the power supply to the heater 207 is feedback-controlled based on temperature information detected by the temperature sensor 263 so that the interior of the processing chamber 201 has a desired temperature distribution (temperature adjustment). Furthermore, the rotation mechanism 267 starts rotating the wafers 200. The evacuation inside the processing chamber 201 and the heating and rotation of the wafers 200 are all continued at least until the processing of the wafers 200 is completed.

[0042] (film formation process) Thereafter, steps A to C are performed in this order to perform a film formation process on the wafer 200. In this specification, the film formation process into the recesses provided on the surface of the wafer 200 is also referred to as a filling process. Each of these steps will be described below.

[0043] [Step A (non-fluid film formation)] In step A, a first reactant (first source material, first reactant) is supplied to wafer 200 in processing chamber 201, i.e., wafer 200 having a recess formed on its surface and an exposed O-containing film, to form a non-fluid film on the surface of wafer 200. In step A, the first source material and the first reactant are supplied under conditions in which, when the first source material is present alone, chemical adsorption or thermal decomposition of the first source material occurs more predominantly than physical adsorption of the first source material.

[0044] Specifically, in step A, a cycle including step A1 of supplying a first raw material to wafer 200 and step A2 of supplying a first reactant to wafer 200 is performed a predetermined number of times (m times, where m is an integer equal to or greater than 1). Step A including steps A1 and A2 will be described in more detail below.

[0045] [Step A1] In step A1, a first source material is supplied to the wafer 200 in the processing chamber 201.

[0046] Specifically, the valve 243a is opened to allow the first source material to flow into the gas supply pipe 232a. The flow rate of the first source material is adjusted by the MFC 241a, and the first source material is supplied into the processing chamber 201 through the nozzle 249a and exhausted from the exhaust port 231a. At this time, the first source material is supplied to the wafers 200 (first source material supply). At this time, the valves 243e to 243g may be opened to supply an inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively.

[0047] After a predetermined time has elapsed, the valve 243a is closed to stop the supply of the first source material into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove gaseous substances remaining in the processing chamber 201. At this time, the valves 243e to 243g are opened to supply an inert gas into the processing chamber 201 through the nozzles 249a to 249c. The inert gas supplied from the nozzles 249a to 249c acts as a purge gas, thereby purging the space in which the wafers 200 exist, i.e., the processing chamber 201.

[0048] The first raw material may be, for example, a silane-based gas containing silicon (Si) as the main element constituting the non-fluid film formed on the surface of the wafer 200. The silane-based gas may be, for example, a gas containing Si and a halogen, i.e., a halosilane-based gas. Halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. The halosilane-based gas may include a chlorosilane-based gas, a fluorosilane-based gas, a bromosilane-based gas, an iodosilane-based gas, etc. The halosilane-based gas may be, for example, a gas containing silicon, carbon (C), and a halogen, i.e., an organic halosilane-based gas. The organic halosilane-based gas may be, for example, a gas containing Si, C, and Cl, i.e., an organic chlorosilane-based gas.

[0049] Examples of the first source material include silane-based gases that do not contain C or halogens, such as monosilane (SiH4, abbreviated as MS) gas and disilane (Si2H6, abbreviated as DS) gas; halosilane-based gases that do not contain C, such as dichlorosilane (SiH2Cl2, abbreviated as DCS) gas and hexachlorodisilane (Si2Cl6, abbreviated as HCDS) gas; alkylsilane-based gases, such as trimethylsilane (SiH(CH3)3, abbreviated as TMS) gas, dimethylsilane (SiH2(CH3)2, abbreviated as DMS) gas, triethylsilane (SiH(C2H5)3, abbreviated as TES) gas, and diethylsilane (SiH2(C2H5)2, abbreviated as DES) gas; and bis(trichlorosilyl)methane ((SiCl3)2CH2, abbreviated as BTCSM) gas and 1,2-bis(trichlorosilyl)methane ((SiCl3)2CH2, abbreviated as BTCSM). Examples of suitable gases that can be used include alkylenehalosilane-based gases such as (chlorosilyl)ethane ((SiCl3)2C2H4, abbreviated as BTCSE) gas, and alkylhalosilane-based gases such as trimethylchlorosilane (SiCl(CH3)3, abbreviated as TMCS) gas, dimethyldichlorosilane (SiCl2(CH3)2, abbreviated as DMDCS) gas, triethylchlorosilane (SiCl(C2H5)3, abbreviated as TECS) gas, diethyldichlorosilane (SiCl2(C2H5)2, abbreviated as DEDCS) gas, 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH3)2Si2Cl4, abbreviated as TCDMDS) gas, and 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH3)4Si2Cl2, abbreviated as DCTMDS) gas.In addition, examples of the first raw material include (dimethylamino)trimethylsilane ((CH3)2NSi(CH3)3, abbreviation: DMATMS) gas, (diethylamino)triethylsilane ((C2H5)2NSi(C2H5)3, abbreviation: DEATES) gas, (dimethylamino)triethylsilane ((CH3)2NSi(C2H5)3, abbreviation: DMATES) gas, (diethylamino)trimethylsilane ((C2H5)2NSi( Examples of usable gases include alkylaminosilane gases such as (CH3)3, abbreviated as DEATMS) gas, (trimethylsilyl)amine ((CH3)3SiNH2, abbreviated as TMSA) gas, (triethylsilyl)amine ((C2H5)3SiNH2, abbreviated as TESA), (dimethylamino)silane ((CH3)2NSiH3, abbreviated as DMAS) gas, and (diethylamino)silane ((C2H5)2NSiH3, abbreviated as DEAS) gas. As the first raw material, one or more of these silicon-containing raw materials can be used.

[0050] Some of these first raw materials do not contain amino groups but contain halogens. Some of these first raw materials contain chemical bonds between silicon and silicon (Si-Si bonds). Some of these first raw materials contain silicon and halogens, or silicon, halogens, and carbon. Some of these first raw materials contain alkyl groups and halogens.

[0051] As the inert gas, nitrogen (N2) gas or a rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas can be used. This also applies to each step described later. As the inert gas, one or more of these can be used.

[0052] [Step A2] In step A2, a first reactant is supplied to the wafer 200 in the process chamber 201.

[0053] Specifically, valve 243b is opened to allow a first reactant to flow into gas supply pipe 232b. The first reactant has its flow rate adjusted by MFC 241b, is supplied into processing chamber 201 via nozzle 249b, and is exhausted from exhaust port 231a. At this time, the first reactant is supplied to wafer 200 (first reactant supply). At this time, valves 243e to 243g may be opened to supply an inert gas into processing chamber 201 via nozzles 249a to 249c, respectively.

[0054] After a predetermined time has elapsed, the valve 243b is closed to stop the supply of the first reactant into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 by a processing procedure similar to the purging in step A1.

[0055] As the first reactant, for example, a nitrogen (N) and hydrogen (H) containing gas can be used. Examples of N and H containing gases include hydrogen nitride gases such as ammonia (NH3) gas, ethylamine gases such as monoethylamine (C2H5NH2, abbreviated as MEA) gas, diethylamine ((C2H5)2NH, abbreviated as DEA) gas, and triethylamine ((C2H5)3N, abbreviated as TEA) gas, methylamine gases such as monomethylamine (CH3NH2, abbreviated as MMA) gas, dimethylamine ((CH3)2NH, abbreviated as DMA) gas, and trimethylamine ((CH3)3N, abbreviated as TMA) gas, pyridine (C5H5N) gas, piperazine (C4H 10Examples of suitable gases include cyclic amine-based gases such as monomethylhydrazine ((CH)HNH, abbreviated as MMH) gas, dimethylhydrazine ((CH)NH, abbreviated as DMH) gas, and trimethylhydrazine ((CH)N(CH)H, abbreviated as TMH) gas. Because amine-based gases and organic hydrazine-based gases are composed of C, N, and H, these gases can also be referred to as C-, N-, and H-containing gases. Amine-based gases containing the alkyl groups described above can also be referred to as alkylamine-based gases. Instead of the C-, N-, and H-containing gas, a C-containing gas (C- and H-containing gas) such as ethylene (CH) gas, acetylene (CH) gas, or propylene (CH) gas, and an N-containing gas (N- and H-containing gas) such as NH may be supplied simultaneously or non-simultaneously. The first reactant can be one or more of these N- and H-containing reactants or C-, N- and H-containing reactants.

[0056] [Perform the specified number of times] The above-mentioned steps A1 and A2 are performed asynchronously, i.e., a predetermined number of times (m times, where m is an integer equal to or greater than 1) under conditions such that, when the first raw material is present alone, chemical adsorption or thermal decomposition of the first raw material occurs more predominantly than physical adsorption of the first raw material.

[0057] The processing conditions for supplying the first raw material in step A1 are as follows: Treatment temperature (first temperature): 350 to 700°C, more preferably 450 to 650°C Treatment pressure: 1 to 2666 Pa, preferably 67 to 1333 Pa First raw material supply flow rate: 0.001 to 2 slm, preferably 0.01 to 1 slm First raw material supply time: 1 to 120 seconds, preferably 1 to 60 seconds Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm, preferably 0.01 to 10 slm is exemplified.

[0058] In this specification, when a numerical range such as "350 to 700°C" is expressed, it means that the lower limit and the upper limit are included in the range. Therefore, for example, "350 to 700°C" means "350°C or higher and 700°C or lower." The same applies to other numerical ranges. In this specification, the processing temperature means the temperature of the wafer 200 or the temperature inside the processing chamber 201, and the processing pressure means the pressure inside the processing chamber 201. A gas supply flow rate of 0 slm means that the gas is not supplied. These also apply to the following explanations.

[0059] The processing conditions for supplying the first reactant in step A2 are: Treatment pressure: 1 to 4000 Pa, preferably 1 to 3000 Pa First reactant supply flow rate: 0.001 to 20 slm, preferably 1 to 10 slm First reactant supply time: 1 to 120 seconds, preferably 1 to 60 seconds Other processing conditions may be the same as the processing conditions when the first raw material is supplied.

[0060] By supplying the first source material in step A1 under the above-described processing conditions, a portion of the molecular structure of the molecules of the first source material can be adsorbed on the surface of the wafer 200 and the surface within the recess, i.e., the surface of the O-containing film, in step A1. Furthermore, by supplying the first reactant in step A2 under the above-described processing conditions, a portion of the molecular structure of the molecules of the first source material adsorbed on the surface of the O-containing film can be reacted with the first reactant to form a non-fluidic layer in step A2. The non-fluidic layer is formed conformally on the surface of the wafer 200 and the surface within the recess, resulting in a layer with high step coverage. Then, by performing the above-described cycle a predetermined number of times under the above-described processing conditions, a non-fluidic film of a predetermined thickness is formed on the surface of the wafer 200 and the surface within the recess, i.e., the surface of the O-containing film.

[0061] The above-mentioned cycle is preferably repeated multiple times. That is, it is preferable to make the thickness of the non-fluidic layer formed per cycle thinner than the desired thickness, and to repeat the above-mentioned cycle multiple times until the thickness of the non-fluidic film formed by laminating the non-fluidic layers reaches the desired thickness. The thickness of the non-fluidic film is preferably equal to or less than the thickness of the fluidic film described later, or thinner than the thickness of the fluidic film described later. The thickness of the non-fluidic film is preferably, for example, 0.2 nm or more and 10 nm or less.

[0062] When the various first raw materials and various first reactants exemplified above are used, it is possible to form, as the non-fluidic film, for example, a Si- and N-containing film such as a silicon nitride film (SiN film) or a Si-, C-, and N-containing film such as a silicon carbonitride film (SiCN film). Since the various first raw materials and various first reactants described above are all O-free, the non-fluidic film is an O-free film. Note that the non-fluidic film is a film with lower hydrophilicity than the O-containing film that serves as the base for the film formation. When the O-containing film that serves as the base for the film formation is a hydrophilic film, it is preferable that the non-fluidic film be a non-hydrophilic film (hydrophobic film).

[0063] [Step B (fluid film formation)] After the non-fluid film is formed on the surface of the wafer 200, the output of the heater 207 is adjusted (temperature drop) so as to change the temperature of the wafer 200 to a second temperature lower than the first temperature. Then, when the temperature of the wafer 200 has reached the second temperature and stabilized, step B is performed.

[0064] In step B, a second reactant (second source, second reactant, third reactant) is supplied to wafer 200 in processing chamber 201, thereby forming a flowable film on the non-flowable film formed by performing step A. In step B, the second source, second reactant, and third reactant are supplied under conditions in which, when the second source is present alone, physical adsorption of the second source occurs more predominantly than chemisorption of the second source without thermal decomposition of the second source.

[0065] Specifically, in step B, a cycle including step B1 of supplying a second raw material to wafer 200, step B2 of supplying a second reactant to wafer 200, and step B3 of supplying a third reactant to wafer 200 is performed a predetermined number of times (n times, n is an integer equal to or greater than 1). Step B, including steps B1 to B3, will be described in more detail below.

[0066] [Step B1] In step B1, the second source material is supplied to the wafer 200 in the processing chamber 201.

[0067] Specifically, the valve 243a is opened to allow the second source material to flow into the gas supply pipe 232a. The flow rate of the second source material is adjusted by the MFC 241a, and the second source material is supplied into the processing chamber 201 through the nozzle 249a and exhausted from the exhaust port 231a. At this time, the second source material is supplied to the wafers 200 (second source material supply). At this time, the valves 243e to 243g may be opened to supply an inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively.

[0068] After a predetermined time has elapsed, the valve 243a is closed to stop the supply of the second source material into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 by a processing procedure similar to the purging in step A1.

[0069] The second source material may be, for example, a silane-based gas containing Si as the main element constituting the flowable film formed on the surface of the wafer 200. The silane-based gas may be, for example, a gas containing Si and a halogen, i.e., a halosilane-based gas. Halogen includes Cl, F, Br, I, etc. The halosilane-based gas may include a chlorosilane-based gas, a fluorosilane-based gas, a bromosilane-based gas, an iodosilane-based gas, etc. The halosilane-based gas may be, for example, a gas containing silicon, carbon, and a halogen, i.e., an organic halosilane-based gas. The organic halosilane-based gas may be, for example, a gas containing Si, C, and Cl, i.e., an organic chlorosilane-based gas.

[0070] Examples of the second source material include C- and halogen-free silane gases such as MS gas and DS gas, C-free halosilane gases such as DCS gas and HCDS gas, alkylsilane gases such as TMS gas, DMS gas, TES gas, and DES gas, alkylenehalosilane gases such as BTCSM gas and BTCSE gas, and alkylhalosilane gases such as TMCS gas, DMDCS gas, TECS gas, DEDCS gas, TCDMDS gas, and DCTMDS gas. The second source material can be one or more of these silicon-containing sources. The second source material can be a source material having the same molecular structure as the first source material.

[0071] Some of these second raw materials do not contain amino groups but contain halogens. Some of these second raw materials contain Si-Si bonds. Some of these second raw materials contain silicon and halogens, or silicon, halogens, and carbon. Some of these second raw materials contain alkyl groups and halogens.

[0072] [Step B2] In step B2, a second reactant is supplied to the wafer 200 in the process chamber 201.

[0073] Specifically, valve 243c is opened to allow the second reactant to flow into gas supply pipe 232c. The flow rate of the second reactant is adjusted by MFC 241c, and the second reactant is supplied into processing chamber 201 via nozzle 249c and exhausted from exhaust port 231a. At this time, the second reactant is supplied to wafer 200 (second reactant supply). At this time, valves 243e to 243g may be opened to supply an inert gas into processing chamber 201 via nozzles 249a to 249c, respectively.

[0074] After a predetermined time has elapsed, the valve 243c is closed to stop the supply of the second reactant into the processing chamber 201. Then, gases remaining in the processing chamber 201 are removed from the processing chamber 201 by a processing procedure similar to the purging in step A1.

[0075] The second reactant may be, for example, a gas containing N and H. Examples of the N and H-containing gas include hydrogen nitride gases such as NH gas, ethylamine gases such as MEA gas, DEA gas, and TEA gas, methylamine gases such as MMA gas, DMA gas, and TMA gas, and CHN gas, CH 10 Cyclic amine-based gases such as N2 gas and organic hydrazine-based gases such as MMH gas, DMH gas, and TMH gas can be used. As described above, these gases can also be referred to as C-, N-, and H-containing gases. The amine-based gases containing the above-mentioned alkyl groups can also be referred to as alkylamine-based gases. Instead of the C-, N-, and H-containing gas, a C-containing gas (C- and H-containing gas) such as C2H4 gas, C2H2 gas, or C3H6 and an N-containing gas (N- and H-containing gas) such as NH3 gas can be supplied simultaneously or non-simultaneously. The second reactant can be one or more of these N- and H-containing reactants or C-, N-, and H-containing reactants. The second reactant can be a reactant having the same molecular structure as the first reactant.

[0076] [Step B3] In step B3, a third reactant is supplied to the wafer 200 in the processing chamber 201.

[0077] Specifically, valve 243d is opened to allow a third reactant to flow into gas supply pipe 232d. The flow rate of the third reactant is adjusted by MFC 241d, and the third reactant is supplied into processing chamber 201 via gas supply pipe 232b and nozzle 249b, and exhausted from exhaust port 231a. At this time, the third reactant is supplied to wafer 200 (third reactant supply). At this time, valves 243e to 243g may be opened to supply an inert gas into processing chamber 201 via nozzles 249a to 249c, respectively.

[0078] After a predetermined time has elapsed, the valve 243d is closed to stop the supply of the third reactant into the processing chamber 201. Then, gases remaining in the processing chamber 201 are removed from the processing chamber 201 by a processing procedure similar to the purging in step A1.

[0079] The third reactant may be, for example, a gas containing N and H. Examples of the N and H-containing gas include hydrogen nitride gases such as NH gas, ethylamine gases such as MEA gas, DEA gas, and TEA gas, methylamine gases such as MMA gas, DMA gas, and TMA gas, and CHN gas, CH 10 Cyclic amine-based gases such as N2 gas and organic hydrazine-based gases such as MMH gas, DMH gas, and TMH gas can be used. As described above, these gases can also be referred to as C-, N-, and H-containing gases. The amine-based gases containing the above-mentioned alkyl groups can also be referred to as alkylamine-based gases. Instead of the C-, N-, and H-containing gas, a C-containing gas (C- and H-containing gas) such as C2H4 gas, C2H2 gas, or C3H6 and an N-containing gas (N- and H-containing gas) such as NH3 gas can be supplied simultaneously or non-simultaneously. The third reactant can be one or more of these N- and H-containing reactants or C-, N-, and H-containing reactants. The third reactant can be a reactant having the same molecular structure as the first reactant.

[0080] [Perform the specified number of times] The above-mentioned steps B1 to B3 are performed asynchronously, i.e., a predetermined number of times (n times, n is an integer equal to or greater than 1) under conditions such that, when the second raw material is present alone, the second raw material is not thermally decomposed and physical adsorption of the second raw material occurs more predominantly than chemisorption of the second raw material.

[0081] The processing conditions for supplying the second raw material in step B1 are as follows: Treatment temperature (second temperature): 0 to 150°C, preferably 10 to 100°C, more preferably 20 to 60°C Treatment pressure: 10 to 6000 Pa, preferably 50 to 2000 Pa Second raw material supply flow rate: 0.01~1slm Second raw material supply time: 1~300 seconds Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm, preferably 0.01 to 10 slm is exemplified.

[0082] The processing conditions for supplying the second reactant in step B2 are: Second reactant supply flow rate: 0.01~5 slm Second reactant supply time: 1 to 300 seconds Other processing conditions may be the same as those used when supplying the second raw material.

[0083] The processing conditions for supplying the third reactant in step B3 are: Third reactant supply flow rate: 0.01~5 slm Third reactant supply time: 1 to 300 seconds Other processing conditions may be the same as those used when supplying the second raw material.

[0084] By performing the above cycle a predetermined number of times under the above processing conditions, oligomers containing elements contained in at least one of the second source material, second reactant, and third reactant are generated, grown, and fluidized, forming an oligomer-containing film as a fluid film on the non-fluid film formed on the surface of the wafer 200 and in the recess, thereby filling the recess with the fluid film. Note that the oligomer refers to a polymer having a relatively low molecular weight (e.g., a molecular weight of 10,000 or less) to which a relatively small number (e.g., 10 to 100) of monomers are bonded. When the above-mentioned second source material, second reactant, and third reactant are used, the non-fluid film can contain, for example, various elements such as Si, Cl, and N, or C atoms such as CH3 and C2H5. x H 2x+1 The film contains a substance represented by the chemical formula (where x is an integer of 1 to 3).

[0085] Furthermore, by performing the cycle including steps B1 to B3 under the above-mentioned processing conditions, it is possible to promote the growth and flow of oligomers formed on the surface of the wafer 200 and in the recesses, while removing and discharging excess components contained in the surface layer of the oligomers or inside the oligomers, such as excess gas, impurities including Cl, and reaction by-products (hereinafter simply referred to as by-products).

[0086] If the processing temperature is set below 0°C, the second source material supplied into the processing chamber 201 is likely to liquefy, making it difficult to supply the second source material in a gaseous state to the wafers 200. In this case, the reaction for forming the flowable film may not proceed smoothly, making it difficult to form a flowable film on a non-flowable film. Setting the processing temperature to 0°C or higher can solve this problem. Setting the processing temperature to 10°C or higher can sufficiently solve this problem, and setting the processing temperature to 20°C or higher can even more sufficiently solve this problem.

[0087] Furthermore, if the processing temperature is higher than 150°C, the reaction for forming the flowable film described above may not proceed smoothly. In this case, the oligomers formed on the non-flowable film may be more likely to detach than grow, making it difficult to form a flowable film on the non-flowable film. This problem can be solved by setting the processing temperature to 150°C or less. This problem can be sufficiently solved by setting the processing temperature to 100°C or less, and even more sufficiently solved by setting the processing temperature to 60°C or less.

[0088] For these reasons, the treatment temperature is desirably set to 0°C or higher and 150°C or lower, preferably 10°C or higher and 100°C or lower, and more preferably 20°C or higher and 60°C or lower.

[0089] [Step C (PT)] After the flowable film is formed on the non-flowable film, the output of the heater 207 is adjusted (heating up) so as to change the temperature of the wafer 200 to a third temperature equal to or higher than the second temperature, preferably to a third temperature higher than the second temperature. Then, when the temperature of the wafer 200 has reached the third temperature and stabilized, step C is performed.

[0090] In step C, an inert gas is supplied to the wafers 200 in the processing chamber 201. Specifically, the valves 243e to 243g are opened to allow the inert gas to flow into the gas supply pipes 232e to 232g. The inert gas has its flow rate adjusted by the MFCs 241e to 241g, is supplied into the processing chamber 201 through the nozzles 249a to 249c, and is exhausted from the exhaust port 231a. At this time, the inert gas is supplied to the wafers 200.

[0091] The processing conditions in step C are as follows: Treatment temperature (third temperature): 100 to 1000°C, preferably 200 to 600°C Treatment pressure: 10 to 80,000 Pa, preferably 200 to 6,000 Pa Inert gas supply flow rate (per gas supply pipe): 0.01 to 2 slm Inert gas supply time: 300 to 10,800 seconds is exemplified.

[0092] By performing step C under the above-described processing conditions, the flowable film formed on the non-flowable film can be modified. This allows the flowable film to be modified so that the non-flowable film fills the recesses formed on the surface, forming a Si- and N-containing film such as a SiN film or a Si, C- and N-containing film such as a SiCN film. Furthermore, while promoting the flow of the flowable film, it is possible to expel excess components contained in the flowable film, thereby densifying the flowable film. By setting the processing temperature (third temperature) in step C to a temperature higher than the processing temperature (first temperature) in step A, it is possible to not only modify the flowable film, but also modify the underlying non-flowable film. That is, it is possible to expel excess components contained in the non-flowable film, thereby densifying the non-flowable film.

[0093] (After purging and atmospheric pressure recovery) After step C is completed, an inert gas is supplied as a purge gas from each of the nozzles 249a to 249c into the processing chamber 201 and exhausted from the exhaust port 231a. This purges the processing chamber 201, and gases and reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (after-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure return).

[0094] (Boat unloading and wafer discharging) Thereafter, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafers 200, supported by the boat 217, are unloaded from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). After the boat unloading, the shutter 219s is moved, and the opening at the lower end of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). After being unloaded to the outside of the reaction tube 203, the processed wafers 200 are removed from the boat 217 (wafer discharge).

[0095] (3) Effects of this mode According to this aspect, one or more of the following effects can be obtained.

[0096] (a) By performing steps A and B in this order and forming a non-fluidic film at a temperature higher than that used for forming the fluidic film before forming a fluidic film on the surface of wafer 200 having recesses formed thereon and exposing the O-containing film, it is possible to block the influence of the surface condition of the O-containing film, which serves as a base for the film formation process. This makes it possible to properly form a fluidic film on the surface of wafer 200 while suppressing abnormal film growth and film formation defects on the surface of wafer 200. As a result, it is possible to improve filling characteristics and achieve void-free and seamless filling with a high-quality film.

[0097] The above-mentioned abnormal growth refers to the growth of a film to be formed on the wafer 200 in a droplet-like (island-like) shape due to the influence of the surface condition of the O-containing film that serves as the base for the film formation process, i.e., the influence of OH (hydroxyl group) termination on the surface of the O-containing film. Abnormal growth may reduce the in-plane film thickness uniformity of the film to be formed on the wafer 200. Abnormal growth may also hinder conformal film formation on the wafer 200 and interfere with filling of recesses, etc. Abnormal growth may also deteriorate the surface roughness (flatness) of the film to be formed on the wafer 200. Abnormal growth may also be a cause of particle generation in the processing chamber 201.

[0098] (b) By making the thickness of the non-fluidic film equal to or less than the thickness of the fluidic film, it is possible to prevent peeling of the non-fluidic film while maintaining the fluidity of the fluidic film.

[0099] If the thickness of the non-fluidic film is less than 0.2 nm, the process of forming the fluidic film may be affected by the surface condition of the O-containing film that serves as the base for the film formation process. That is, if the thickness of the non-fluidic film is too thin, the non-fluidic film may not be able to sufficiently block the effect of blocking the influence of the surface condition of the O-containing film. In this case, abnormal film growth on the surface of the wafer 200, i.e., film formation failure, may occur.

[0100] In contrast, by setting the thickness of the non-fluidity film to 0.2 nm or more, it is possible to sufficiently block the influence of the surface state of the O-containing film on the process of forming the fluidity film. In other words, by providing the non-fluidity film with an appropriate thickness, it is possible to sufficiently exhibit the effect of blocking the influence of the surface state of the O-containing film by the non-fluidity film. This makes it possible to sufficiently suppress abnormal growth of the film on the surface of the wafer 200, i.e., the occurrence of film formation defects.

[0101] Furthermore, by making the thickness of the non-fluidic film 0.5 nm or more, the blocking effect of the non-fluidic film on the influence of the surface state of the O-containing film can be further enhanced, and the above-mentioned effects can be more fully obtained. Also, by making the thickness of the non-fluidic film 1.5 nm or more, the blocking effect of the non-fluidic film on the influence of the surface state of the O-containing film can be further enhanced, and the above-mentioned effects can be more fully obtained.

[0102] For these reasons, it is desirable that the thickness of the non-fluid film is 0.2 nm or more, preferably 0.5 nm or more, and more preferably 1.5 nm or more.

[0103] Furthermore, if the thickness of the non-fluidic film is greater than 10 nm, film peeling may occur, which may lead to particle generation and film formation defects. That is, if the non-fluidic film is made too thick, although the blocking effect described above is enhanced, film peeling may have an adverse effect on film formation.

[0104] In contrast, by setting the thickness of the non-fluidic film to 10 nm or less, it is possible to sufficiently suppress the occurrence of film peeling, and it is possible to suppress the generation of particles and film formation defects caused by this film peeling. In other words, by providing the non-fluidic film with an appropriate thickness, it is possible to sufficiently suppress the occurrence of film peeling, and it is possible to prevent the occurrence of adverse effects on film formation caused by it.

[0105] By setting the thickness of the non-fluidic film to 5 nm or less, the effect of suppressing film peeling can be further increased, and the above-mentioned effects can be more fully achieved. Also, by setting the thickness of the non-fluidic film to 3 nm or less, the effect of suppressing film peeling can be further increased, and the above-mentioned effects can be more fully achieved.

[0106] For these reasons, it is desirable that the thickness of the non-fluid film is 10 nm or less, preferably 5 nm or less, and more preferably 3 nm or less.

[0107] Considering these points, it is desirable that the thickness of the non-fluid film is, for example, 0.2 nm or more and 10 nm or less, preferably 0.5 nm or more and 5 nm or less, and more preferably 1.5 nm or more and 3 nm or less.

[0108] (c) When the O-containing film serving as the base for film formation is a Si- and O-containing film, this film has many OH (hydroxyl group) terminations on the surface, and the above-mentioned effects are particularly pronounced.

[0109] (d) The above-described effect is particularly pronounced when the non-fluidic film to be formed on the wafer 200 is an O-free film. For example, when the non-fluidic film to be formed on the wafer 200 is an Si- and N-containing film or an Si, C- and N-containing film, the above-described effect is particularly pronounced.

[0110] (e) The above-described effect is particularly pronounced when the non-fluidic film to be formed on the wafer 200 is less hydrophilic than the O-containing film that serves as a base for the film formation. Also, when the O-containing film that serves as a base for the film formation is a hydrophilic film and the non-fluidic film to be formed thereon is a non-hydrophilic film (hydrophobic film), the above-described effect is particularly pronounced.

[0111] (f) In step A, by supplying the first source and the first reactant to the wafer 200 under conditions in which chemical adsorption or thermal decomposition of the first source occurs more predominantly than physical adsorption of the first source when the first source is present alone, it is possible to efficiently form a non-fluid film on the wafer 200.

[0112] (g) In step A, by performing a cycle including steps A1 and A2 a predetermined number of times (m times, where m is an integer equal to or greater than 1), it becomes possible to form a non-fluidic film with good controllability on the wafer 200. Also, in step A, by performing a cycle in which steps A1 and A2 are performed non-simultaneously a predetermined number of times, it becomes possible to form a non-fluidic film with better controllability on the wafer 200.

[0113] Furthermore, in step A, by performing a cycle including step A1 of adsorbing a part of the molecular structure of the molecules of the first raw material onto the surface of the O-containing film and step A2 of reacting the part of the molecular structure of the molecules of the first raw material adsorbed onto the surface of the O-containing film with the first reactant to form a non-fluidity layer a predetermined number of times, it becomes possible to form a non-fluidity film in which non-fluidity layers formed per cycle are stacked, and it becomes possible to form the non-fluidity film with better controllability.

[0114] (h) When at least one of the first source material and the first reactant contains an alkyl group, that is, when the first reactant contains an alkyl group, it becomes possible to efficiently cause a reaction for forming a non-fluidic film on the surface of the wafer 200. Furthermore, when the first reactant contains an alkyl group, it becomes possible to further enhance the blocking effect of the non-fluidic film on the influence of the surface state of the O-containing film.

[0115] (i) In step B, when the second source exists alone, by supplying the second source, the second reactant, and the third reactant to the wafer 200 under conditions in which the second source does not thermally decompose and the physical adsorption of the second source occurs more predominantly than the chemical adsorption of the second source, it is possible to efficiently form a fluid film on the wafer 200.

[0116] (j) In step B, a flowable film can be formed on the wafer 200 with good controllability by performing a cycle including steps B1 to B3 a predetermined number of times (n times, where n is an integer of 1 or more).

[0117] (k) In step B, oligomers containing elements contained in at least one of the second raw material, the second reactant, and the third reactant are generated, grown, and made to flow, thereby enabling the formation of an appropriate flowable film on the non-flowable film. Note that while oligomers are generated in step B, oligomers are not generated in step A.

[0118] (l) In step B, by differentiating the molecular structures of the second reactant and the third reactant, each reactant can have a different role. By using, for example, an amine-based gas as the second reactant, this reactant can act as a catalyst, and by performing step B1, the second source material physically adsorbed on the surface of the wafer 200 can be activated. Furthermore, by using, for example, a hydrogen nitride-based gas as the third reactant, this reactant can act as an N source, allowing N to be incorporated into the flowable film.

[0119] (m) In step C, by performing post-treatment on the wafer 200 after a fluid film has been formed on the non-fluid film at a third temperature higher than the second temperature, it is possible to promote the fluidity of the fluid film and improve the filling characteristics of the film formed in the recess.

[0120] Furthermore, in step C, the flow of the fluid film is promoted while the excess components contained in the fluid film are discharged, and the fluid film is densified, thereby improving the filling characteristics of the film formed in the recess. Furthermore, the impurity concentration of the film formed to fill the recess can be reduced, and further, the film density can be increased. These factors make it possible to improve the wet etching resistance of the film formed in the recess.

[0121] Furthermore, in step C, supplying an inert gas to the wafer 200 promotes the flow of the fluid film, thereby improving the filling characteristics of the film formed in the recesses. This also reduces the impurity concentration of the film formed to fill the recesses, and further increases the film density. These factors improve the wet etching resistance of the film formed in the recesses.

[0122] (n) By making the molecular structure of the first raw material the same as the molecular structure of the second raw material and the molecular structure of the first reactant the same as the molecular structure of either the second reactant or the third reactant, i.e., by forming a non-fluidic film and a fluidic film using the same raw material and reactant in steps A and B, the structure can be simplified, such as by reducing the number of supply lines in the reactant supply system, and an increase in equipment costs can be suppressed.

[0123] (o) When the first source material and the second source material are silicon-containing sources, and the first reactant, the second reactant and the third reactant are N- and H-containing reactants or C, N- and H-containing reactants, the above-mentioned effects are particularly pronounced.

[0124] (p) By performing steps A and B in the same processing chamber (in-situ), it is possible to continuously form a non-fluidic film and a fluidic film, and the interface between the non-fluidic film and the fluidic film can be kept clean, making it possible to suppress deterioration of film properties and electrical properties. If the non-fluidic film and the fluidic film are formed in different processing chambers (ex-situ), the non-fluidic film is exposed to the atmosphere outside the processing chamber, for example, the air, which can trap moisture and impurities in the air at the interface between the non-fluidic film and the fluidic film, making it difficult to maintain the interface clean. In this case, the film properties and electrical properties can be deteriorated due to the interface condition.

[0125] (q) In step A, a non-fluidic film is formed on the surface of the wafer 200 and the surface of the recessed portion, and in step B, a fluidic film is formed on the non-fluidic film formed on the surface of the wafer 200 and in the recessed portion, and the recessed portion is filled with the fluidic film, thereby achieving the above-mentioned effects. As a result, it is possible to improve filling characteristics while suppressing abnormal growth of the film on the surface of the wafer 200, and to achieve void-free and seamless filling with a high-quality film.

[0126] (r) According to this embodiment, a series of processes can be performed in a non-plasma atmosphere, making it possible to prevent plasma damage to the wafer 200 and the like.

[0127] (s) The above-mentioned effects can be similarly obtained when the above-mentioned various raw materials, reactants, and inert gases are used in steps A and B. The above-mentioned effects can also be similarly obtained even when the gas supply order in the cycle is changed. The above-mentioned effects can also be similarly obtained when the above-mentioned various inert gases are used in step C.

[0128] <Second Aspect of the Present Disclosure> Next, a second embodiment of the present disclosure will be described mainly with reference to FIG.

[0129] As shown in Figure 5 and the processing sequence below, in step B, simultaneously supplying a second source material to the wafer 200 and supplying a second reactant to the wafer 200; applying a third reactant to the wafer 200; Alternatively, a cycle of non-simultaneously performing the above may be performed a predetermined number of times (n times, n is an integer of 1 or more).

[0130] (First raw material → First reactant) × m → (Second raw material + Second reactant → Third reactant) × n → PT

[0131] According to this aspect, the same effects as those of the first aspect can be obtained. Furthermore, in this aspect, since the second source material and the second reactant are supplied simultaneously, it is possible to improve the cycle rate and increase the productivity of substrate processing. The processing conditions when the second source material and the second reactant are supplied simultaneously can be the same as the processing conditions when the second reactant is supplied in step B2 described above.

[0132] <Third Aspect of the Present Disclosure> Next, a third embodiment of the present disclosure will be described mainly with reference to FIG.

[0133] As shown in Figure 6 and the processing sequence below, in Step B, simultaneously supplying a second source material to the wafer 200 and supplying a second reactant to the wafer 200; applying a third reactant to the wafer 200; applying a second reactant to the wafer 200; Alternatively, a cycle of non-simultaneously performing the above may be performed a predetermined number of times (n times, n is an integer of 1 or more).

[0134] (First raw material → First reactant) × m → (Second raw material + Second reactant → Third reactant → Second reactant) × n → PT

[0135] According to this aspect, the same effects as those of the first aspect can be obtained. Furthermore, in this aspect, by using, for example, an amine-based gas as the second reactant, the second reactant flowed in the first cycle can act as a catalyst to activate the second source material. Furthermore, the second reactant flowed in the second cycle can act as a gas that removes by-products generated during the film formation process, i.e., a reactive purge gas. The processing conditions for supplying these second reactants can be the same as the processing conditions for supplying the second reactant in step B2 described above.

[0136] <Other Aspects of the Present Disclosure> Although various aspects of the present disclosure have been specifically described above, the present disclosure is not limited to the above-described aspects and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0137] For example, when a source containing Si, C, and N, such as an alkylaminosilane gas, is used as the first source, only the first source may be used as the first reactant in step A, without using the first reactant. That is, in step A, the first source may be supplied to a substrate having a recess formed on its surface and an exposed O-containing film at a first temperature without supplying the first reactant. In this case, the first source may be supplied alone as the reactive substance, or an inert gas may be supplied simultaneously. The processing procedure and processing conditions for supplying the first source may be the same as those in step A1 of the above-described embodiment. Even in this case, by performing step A, a non-fluid film can be formed on the surface of the substrate, and the same effects as those of the above-described embodiment can be obtained.

[0138] In this case, if the first source material is supplied to the substrate under conditions where a self-limit occurs in the adsorption of the first source material onto the surface of the substrate, a part of the molecular structure of the molecules of the first source material is adsorbed (chemically adsorbed) onto the surface of the O-containing film, and a non-fluidic film containing Si, C, and N and having a thickness of one monolayer is formed on the surface of the substrate by performing step A. In this case, if the first source material is supplied to the substrate under conditions where a self-limit does not occur in the adsorption of the first source material onto the surface of the substrate, the first source material is decomposed, and a non-fluidic film containing Si, C, and N and having a thickness of more than one monolayer is formed on the surface of the substrate by performing step A.

[0139] Further, for example, the reactants (first reactant, second reactant, third reactant) may be, in addition to the above-mentioned N- and H-containing gas or C-, N-, and H-containing gas, C- and H-containing gases such as ethylene (C2H4) gas, acetylene (C2H2) gas, and propylene (C3H6) gas, or boron (B)- and H-containing gases such as diborane (B2H6) gas and trichloroborane (BCl3) gas. Using these reactants, SiN films, SiCN films, and non-O-containing films containing Si, such as silicon carbide films (SiC films), silicon boron nitride films (SiBN films), and silicon boron carbonitride films (SiBCN films), may be formed on a substrate through the above-mentioned processing sequence. The processing procedures and processing conditions for supplying raw materials and reactants may be similar to those in each step of the above-mentioned aspects. In these cases, the film types of the non-fluidic film and the fluidic film may be different. For example, when a SiN film, a SiCN film, or the like is formed as the flowable film, a SiC film, a SiBN film, a SiBCN film, or the like may be formed as the non-flowable film in addition to the SiN film or the SiCN film. In these cases, the same effects as those of the above-mentioned embodiment can be obtained.

[0140] Furthermore, for example, raw material gases containing metal elements such as aluminum (Al), titanium (Ti), hafnium (Hf), zirconium (Zr), tantalum (Ta), molybdenum (Mo), and tungsten (W) are used as raw materials (first raw material, second raw material), and by the above-mentioned processing sequence, an aluminum nitride film (AlN film), a titanium nitride film (TiN film), a hafnium nitride film (HfN film), a zirconium nitride film (ZrN film), a tantalum nitride film (TaN film), a molybdenum nitride film (MoN), a tungsten nitride film (WN film), a tantalum nitride film (TaN film), a molybdenum nitride film (MoN), a tungsten nitride film (WN film), a tantalum nitride film (TaN film), a tungsten nitride film (WN film), a titanium nitride film (TiN film), a hafnium nitride film (HfN film), a zirconium nitride film (ZrN film), a tantalum nitride film (TaN film), a molybdenum nitride film (MoN), a tungsten nitride film (WN film), a tantalum nitride film (TaN film), a tantalum nitride film (MoN film ... The present disclosure can also be applied to the formation of films containing metal elements, such as a titanium carbonitride film (WN), an aluminum carbonitride film (AlCN), a titanium carbonitride film (TiCN), a hafnium carbonitride film (HfCN), a zirconium carbonitride film (ZrCN), a tantalum carbonitride film (TaCN), a molybdenum carbonitride film (MoCN), a tungsten carbonitride film (WCN), a titanium aluminum nitride film (TiAlN), a titanium aluminum carbonitride film (TiAlCN), and a titanium aluminum carbide film (TiAlC). The processing procedures and processing conditions for supplying raw materials and reactants can be similar to those in each step of the above-described embodiment. In these cases, the film types of the non-flowable film and the flowable film may be different. For example, when a SiN film, a SiCN film, or the like is formed as the flowable film, an AlN film, a TiN film, a HfN film, a ZrN film, a TaN film, a MoN, a WN, an AlCN film, a TiCN film, a HfCN film, a ZrCN film, a TaCN film, a MoCN, a WCN, a TiAlN film, a TiAlCN film, a TiAlC film, or the like may be formed as the non-flowable film. In these cases, the same effects as those of the above-mentioned embodiment can be obtained.

[0141] Furthermore, for example, in PT, an H-containing gas such as hydrogen (H) gas may be supplied to the substrate, an N-containing gas such as NH gas, i.e., an N- and H-containing gas, or an O-containing gas such as HO gas, i.e., an O- and H-containing gas, may be supplied. Note that O gas may be supplied as the O-containing gas. That is, in PT, at least one of an N-containing gas, an H-containing gas, an N- and H-containing gas, an O-containing gas, or an O- and H-containing gas may be supplied to the substrate.

[0142] The processing conditions for supplying H-containing gas in PT are as follows: H-containing gas supply flow rate: 0.01 to 3 slm Treatment pressure: 10 to 1000 Pa, preferably 200 to 800 Pa Other processing conditions may be the same as those in step C above.

[0143] The processing conditions for supplying N and H containing gas in PT are as follows: N and H-containing gas supply flow rate: 10 to 10,000 sccm Treatment pressure: 10 to 6000 Pa, preferably 200 to 2000 Pa Other processing conditions may be the same as those in step C above.

[0144] The processing conditions for supplying O-containing gas in PT are as follows: O-containing gas supply flow rate: 10 to 10,000 sccm Treatment pressure: 10 to 90,000 Pa, preferably 20,000 to 80,000 Pa Other processing conditions may be the same as those in step C above.

[0145] Even in these cases, the same effects as those of the first aspect can be obtained. It should be noted that performing PT under an H-containing gas atmosphere or an N- and H-containing gas atmosphere can increase the fluidity of the oligomer-containing layer and improve the filling characteristics of the film formed in the recesses compared to performing PT under an inert gas atmosphere. Furthermore, performing PT under an H-containing gas atmosphere or an N- and H-containing gas atmosphere can reduce the impurity concentration of the film formed in the recesses, increase the film density, and improve the wet etching resistance compared to performing PT under an inert gas atmosphere. It should be noted that performing PT under an N- and H-containing gas atmosphere can enhance these effects compared to performing PT under an H-containing gas atmosphere. Furthermore, performing PT under an O-containing gas atmosphere can incorporate O into the film obtained by modifying the oligomer-containing layer, enabling the film to be a silicon oxynitride carbonitride film (SiOCN film) containing Si, O, C, and N.

[0146] Furthermore, for example, the present disclosure can be applied not only to the case where the O-containing film exposed on the surface of the substrate is an SiO film, but also to the case where it is a silicon oxynitride film (SiON film), a silicon oxycarbide film (SiOC film), or a silicon oxycarbonitride film (SiOCN film). That is, when an OH termination exists on the surface of the O-containing film exposed on the surface of the substrate, the present disclosure can be applied, and the same effects as those of the above-mentioned embodiment can be obtained.

[0147] Up to this point, examples have been described in which SiN films, SiCN films, SiOCN films, etc. are formed to fill recesses formed on the surface of a substrate, but the present disclosure is not limited to these examples. That is, by arbitrarily combining the gases used in the first reactant, second reactant, and PT, it is also possible to form films such as SiO films, SiOC films, and Si films to fill recesses formed on the surface of a substrate. In these cases, the same effects as those in the above-mentioned embodiment can be obtained.

[0148] The present disclosure can be suitably applied to, for example, forming STI (Shallow Trench Isolation), PMD (Pre-Metal dielectric), IMD (Inter-metal dielectric), ILD (Inter-layer dielectric), Gate Cut fill, etc.

[0149] It is preferable that recipes used for substrate processing are individually prepared according to the processing content and stored in the storage device 121c via an electric communication line or the external storage device 123. Then, when starting processing, it is preferable that the CPU 121a appropriately selects an appropriate recipe from the multiple recipes stored in the storage device 121c according to the substrate processing content. This makes it possible to reproducibly form films with various film types, composition ratios, film qualities, and film thicknesses using a single substrate processing device. It also reduces the burden on the operator, prevents operational errors, and enables processing to be started quickly.

[0150] The above-mentioned recipes do not necessarily have to be newly created, but may be prepared by modifying an existing recipe already installed in the substrate processing apparatus, for example. When modifying a recipe, the modified recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium on which the modified recipe is recorded. Alternatively, an existing recipe already installed in the substrate processing apparatus may be directly modified by operating the input / output device 122 provided in the existing substrate processing apparatus.

[0151] In the above-described embodiment, an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at a time has been described. The present disclosure is not limited to the above-described embodiment and can be suitably applied, for example, to a case where a film is formed using a single-wafer substrate processing apparatus that processes one or several substrates at a time. Furthermore, in the above-described embodiment, an example of forming a film using a substrate processing apparatus having a hot-wall processing furnace has been described. The present disclosure is not limited to the above-described embodiment and can be suitably applied to a case where a film is formed using a substrate processing apparatus having a cold-wall processing furnace.

[0152] When using these substrate processing apparatuses, film formation can be performed using the same sequence and processing conditions as in the above-described embodiments and modifications, and the same effects as in the above-described embodiments and modifications can be obtained.

[0153] The above-described embodiments and modifications may be used in combination as appropriate. The processing procedures and processing conditions in such a case may be the same as those of the above-described embodiments and modifications, for example. [Example]

[0154] As an example, a film formation process was performed on a wafer having recesses on its surface and an exposed O-containing film by the process sequence of the first embodiment (non-fluidic film formation, fluidic film formation, and post-treatment) using the substrate processing apparatus shown in Fig. 1. The process conditions in each step were set to predetermined conditions within the range of process conditions in each step of the process sequence of the first embodiment.

[0155] As a comparative example, a film formation process was performed on a wafer in which recesses were formed on the surface and an O-containing film was exposed by performing the flowable film formation and post-treatment of the processing sequence of the first embodiment using the substrate processing apparatus shown in Fig. 1. The processing conditions in each step were the same as those in the example.

[0156] The wafer surfaces after the film formation process in the example and comparative example were then observed to check for the occurrence of abnormal growth. The results are shown in Figures 7, 8(a), and 8(b). As shown in Figures 7 and 8(a), in the example in which a non-fluidic film was formed before forming the fluidic film, no abnormal growth of the fluidic film was observed. In contrast, as shown in Figures 7 and 8(b), in the comparative example in which a non-fluidic film was not formed before forming the fluidic film, abnormal growth of the fluidic film was observed. [Explanation of symbols]

[0157] 200 wafers (substrates) 201 Processing Room

Claims

1. (a) forming a non-flowable film on a surface of a substrate, the surface of the substrate having a recess and an oxygen-containing film having OH termination exposed thereon, by supplying a first reactant at a first temperature to the substrate; (b) providing a second reactant to the substrate at a second temperature lower than the first temperature to form a flowable film on the non-flowable film, the flowable film being oxygen-free; (c) performing a post-treatment on the substrate after the flowable film has been formed on the non-flowable film under an atmosphere of at least one of an inert gas, a hydrogen gas, and a nitrogen and hydrogen-containing gas to promote the flowability of the flowable film and modify the flowable film into a densified oxygen-free film; A substrate processing method comprising:

2. 2. The substrate processing method according to claim 1, wherein the thickness of the non-fluidic film is set to be equal to or less than the thickness of the fluidic film, or thinner than the thickness of the fluidic film.

3. 2. The substrate processing method according to claim 1, wherein the thickness of the non-fluidic film is set to 0.2 nm or more and 10 nm or less.

4. 4. The substrate processing method according to claim 1, wherein the oxygen-containing film is a silicon and oxygen-containing film.

5. 4. The substrate processing method according to claim 1, wherein the non-fluidic film is an oxygen-free film.

6. 4. The substrate processing method according to claim 1, wherein the non-fluidic film is a film containing silicon and nitrogen.

7. 4. The substrate processing method according to claim 1, wherein the non-fluidic film is a film containing silicon, carbon, and nitrogen.

8. 4. The substrate processing method according to claim 1, wherein the non-fluidic film is less hydrophilic than the oxygen-containing film.

9. 4. The substrate processing method according to claim 1, wherein the oxygen-containing film is a hydrophilic film, and the non-fluidic film is a non-hydrophilic film.

10. the first reactant comprises a first source and a first reactant; 4. The substrate processing method according to claim 1, wherein in step (a), the first source and the first reactant are supplied to the substrate under conditions such that, when the first source is present alone, chemical adsorption or thermal decomposition of the first source occurs more predominantly than physical adsorption of the first source.

11. 11. The substrate processing method of claim 10, wherein (a) comprises a cycle including: (a1) supplying the first source material to the substrate; and (a2) supplying the first reactant to the substrate, the cycle being performed a predetermined number of times.

12. 12. The substrate processing method of claim 11, wherein in (a1), a portion of the molecular structure of the molecules of the first source is adsorbed onto the surface of the oxygen-containing film, and in (a2), the portion of the molecular structure of the molecules of the first source adsorbed onto the surface of the oxygen-containing film is reacted with the first reactant to form a non-fluid layer.

13. 11. The substrate processing method of claim 10, wherein at least one of the first source and the first reactant includes an alkyl group.

14. 4. The substrate processing method according to claim 1, wherein the first reactant includes an alkyl group.

15. The substrate processing method according to any one of claims 1 to 3, wherein the second reactant includes a second source, a second reactant, and a third reactant, and in (b), the second source, the second reactant, and the third reactant are supplied to the substrate in a non-plasma atmosphere under conditions such that, when the second source is present alone, physical adsorption of the second source occurs more predominantly than chemisorption of the second source without thermal decomposition of the second source.

16. 16. The substrate processing method of claim 15, wherein (b) comprises a cycle including the steps of: (b1) supplying the second source material to the substrate; (b2) supplying the second reactant to the substrate; and (b3) supplying the third reactant to the substrate, the cycle being performed a predetermined number of times.

17. 16. The substrate processing method of claim 15, wherein in step (b), oligomers containing an element contained in at least one of the second source material, the second reactant, and the third reactant are generated, grown, and fluidized to form an oligomer-containing film as the fluidized film on the non-fluidized film.

18. 4. The substrate processing method according to claim 1, wherein in (c), the post-treatment is performed on the substrate at a third temperature higher than the second temperature.

19. The first reactant comprises a first raw material and a first reactant; 16. The substrate processing method of claim 15, wherein the first source has the same molecular structure as the second source, and the first reactant has the same molecular structure as either the second reactant or the third reactant.

20. The first reactant comprises a first raw material and a first reactant; 16. The substrate processing method of claim 15, wherein the first source and the second source are silicon-containing sources, and the first reactant, the second reactant, and the third reactant are nitrogen- and hydrogen-containing reactants or carbon-, nitrogen-, and hydrogen-containing reactants.

21. 4. The substrate processing method according to claim 1, wherein steps (a) and (b) are carried out in the same processing chamber.

22. 4. The substrate processing method according to claim 1, wherein (a) the non-fluidic film is formed on the surface of the substrate and the surface of the recess, and (b) the fluidic film is formed on the non-fluidic film formed on the surface of the substrate and in the recess, and the recess is filled with the fluidic film.

23. (a) forming a non-flowable film on a surface of a substrate, the surface of the substrate having a recess and an oxygen-containing film having OH termination exposed thereon, by supplying a first reactant at a first temperature to the substrate; (b) providing a second reactant to the substrate at a second temperature lower than the first temperature to form a flowable film on the non-flowable film, the flowable film being oxygen-free; (c) performing a post-treatment on the substrate after the flowable film has been formed on the non-flowable film under an atmosphere of at least one of an inert gas, a hydrogen gas, and a nitrogen and hydrogen-containing gas to promote the flowability of the flowable film and modify the flowable film into a densified oxygen-free film; A method for manufacturing a semiconductor device having the above structure.

24. a first reactant supply system that supplies a first reactant to the substrate; a second reactant supply system that supplies a second reactant to the substrate; an inert gas supply system for supplying an inert gas to the substrate; a heater for heating the substrate; a control unit configured to be able to control the first reactant supply system, the second reactant supply system, the inert gas supply system, and the heater so as to perform the following processes: (a) a process of forming a non-fluidic film on a surface of a substrate, the surface of which has recesses and an oxygen-containing film having OH termination exposed thereon, by supplying the first reactant at a first temperature; (b) a process of forming an oxygen-free flowable film on the non-fluidic film by supplying a second reactant to the substrate at a second temperature lower than the first temperature; and (c) a process of promoting the fluidity of the flowable film and modifying the flowable film into a densified oxygen-free film by performing post-treatment in an inert gas atmosphere on the substrate after the flowable film has been formed on the non-fluidic film; A substrate processing apparatus having:

25. (a) forming a non-flowable film on a surface of a substrate by supplying a first reactant to the substrate at a first temperature, the first reactant being provided on the surface of the substrate, the first reactant having an oxygen-containing film with OH termination exposed on the surface; (b) providing a second reactant to the substrate at a second temperature lower than the first temperature to form a flowable film on the non-flowable film, the flowable film being oxygen-free; (c) performing a post-treatment on the substrate after the flowable film has been formed on the non-flowable film under an atmosphere of at least one of an inert gas, a hydrogen gas, and a nitrogen and hydrogen-containing gas, thereby promoting the flowability of the flowable film and modifying the flowable film into a densified oxygen-free film; A program that causes a computer to execute the above in a substrate processing apparatus.

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