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

Abstract

The present invention comprises: (a) a process of performing a cycle of a process including supplying a raw material gas to a substrate having recessed portions formed on its surface, a process including supplying a first nitrogen and hydrogen-containing gas to the substrate, and a process including supplying a second nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers of elements contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to be generated, grow, and flow on the surface and in the recessed portions of the substrate, thereby forming an oligomer-containing layer on the surface and in the recessed portions of the substrate; and (b) a process of post-treating the substrate having the oligomer-containing layer formed on the surface and in the recessed portions of the substrate at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface and in the recessed portions of the substrate, thereby forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recessed portions.

Description

Technical Field

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

[0002] As one of the manufacturing processes of semiconductor devices, a film is formed on a substrate using multiple gases (see, for example, Patent Documents 1 and 2). In this process, the film is formed using multiple gases so as to be embedded in recesses provided on the substrate surface.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2017-34196

[0006] Patent Document 2: Japanese Patent Application Laid-Open No. 2013-30752 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] An object of the present disclosure is to improve the characteristics of a film formed so as to be embedded in a recess provided on a substrate surface.

[0009] Solutions to Problems

[0010] According to one embodiment of the present disclosure, a technology is provided that performs the following steps:

[0011] (a) a step of performing a cycle comprising a step of supplying a raw material gas to a substrate having a recessed portion formed on its surface, a step of supplying a first nitrogen and hydrogen-containing gas to the substrate, and a step of supplying a second nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers containing an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recessed portion, thereby forming an oligomer-containing layer on the surface of the substrate and in the recessed portion; and

[0012] (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recess.

[0013] Effects of the Invention

[0014] According to the present disclosure, it is possible to improve the characteristics of a film formed so as to be embedded in a recess provided in a substrate surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is a schematic structural diagram of a vertical processing furnace of a substrate processing apparatus preferably used in each embodiment of the present disclosure, showing the processing furnace portion in a longitudinal cross-sectional view.

[0016] Figure 2 This is a schematic structural diagram of a vertical processing furnace of a substrate processing device preferably used in each embodiment of the present invention. Figure 1 The sectional view along line AA shows the processing furnace portion.

[0017] Figure 3 This is a schematic structural diagram of a controller of a substrate processing apparatus preferably used in each embodiment of the present disclosure, and shows the control system of the controller in a block diagram.

[0018] Figure 4 It is a diagram showing a substrate processing sequence according to the first embodiment of the present disclosure.

[0019] Figure 5 It is a diagram showing a substrate processing sequence according to the second embodiment of the present disclosure.

[0020] Figure 6 It is a diagram showing a substrate processing sequence according to the third embodiment of the present disclosure. DETAILED DESCRIPTION

[0021] <First aspect of the present disclosure>

[0022] The following reference Figures 1 to 4 A first embodiment of the present disclosure will be described.

[0023] (1) Structure of substrate processing apparatus

[0024] like Figure 1 As shown, the processing furnace 202 includes a heater 207 as a heating mechanism (temperature adjustment unit). The heater 207 is cylindrical and is supported by a holding plate and installed vertically. The heater 207 also functions as an activation mechanism (excitation unit) that thermally activates (excites) the gas.

[0025] A reaction tube 203 is arranged 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. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS) and 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 mounted vertically, similar to the heater 207. The reaction tube 203 and the manifold 209 primarily constitute the processing vessel (reaction container). The processing chamber 201 is formed within the hollow portion of the processing vessel. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. The wafer 200 is processed in the processing chamber 201 .

[0026] Within processing chamber 201, nozzles 249a to 249c, serving as first to third gas supply units, are installed so as to penetrate the sidewalls of manifold 209. These nozzles 249a to 249c are also referred to as first to third nozzles. These nozzles 249a to 249c are made of a heat-resistant material, such as quartz or SiC, or a non-metallic material. These nozzles 249a to 249c are connected to gas supply pipes 232a to 232c, respectively. These nozzles 249a to 249c are distinct nozzles, with nozzles 249a and 249c located adjacent to nozzle 249b.

[0027] Gas supply pipes 232a to 232c are provided, in order from the upstream side of the gas flow, with mass flow controllers (MFCs) 241a to 241c, serving as flow controllers (flow control units), and valves 243a to 243c, serving as on-off valves. Gas supply pipe 232e is connected downstream of valve 243a of gas supply pipe 232a. Gas supply pipes 232d and 232f are connected downstream of valve 243b of gas supply pipe 232b, respectively. Gas supply pipe 232g is connected downstream of valve 243c of gas supply pipe 232c. MFCs 241d to 241g and valves 243d to 243g are provided, 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.

[0028] like Figure 2As shown, nozzles 249a-249c are each positioned in a circular space between the inner wall of reaction tube 203 and wafers 200, extending upward from the bottom to the top of the inner wall of reaction tube 203, in a manner extending upward in the direction in which wafers 200 are arranged. Specifically, nozzles 249a-249c are each positioned along the wafer arrangement area, lateral to and horizontally surrounding the wafer arrangement area where wafers 200 are arranged. When viewed from above, nozzle 249b is positioned so as to be aligned with exhaust port 231a (described later) across the center of wafer 200 loaded into processing chamber 201. Nozzles 249a and 249c are positioned so as to sandwich a straight line L along the inner wall of reaction tube 203 (the outer periphery of wafer 200) from both sides. This straight line L passes through the center of nozzle 249b and exhaust port 231a. This straight line L also passes through the center of nozzle 249b and wafer 200. That is, nozzle 249c is disposed on opposite sides of nozzle 249a across line L. Nozzles 249a and 249c are arranged symmetrically with line L as the axis of symmetry. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of nozzles 249a to 249c, respectively. Each of gas supply holes 250a to 250c opens so as to face exhaust port 231a when viewed from above, and is capable of supplying gas toward wafer 200. A plurality of gas supply holes 250a to 250c are provided from the bottom to the top of reaction tube 203.

[0029] As a raw material gas, for example, a silane gas is supplied from the gas supply pipe 232a via the MFC 241a, the valve 243a, and the nozzle 249a into the processing chamber 201. The gas contains silicon (Si), which is the main element constituting the film formed on the surface of the wafer 200. As the silane gas, a gas containing Si and halogen, i.e., a halosilane gas, can be used. Halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. As the halosilane gas, for example, a gas containing silicon, carbon (C) and halogen, i.e., an organohalosilane gas, can be used. As the organohalosilane gas, for example, a gas containing Si, C and Cl, i.e., an organochlorosilane gas, can be used.

[0030] As the first nitrogen (N) and hydrogen (H) containing gas, for example, amine gas is supplied from gas supply pipe 232b via MFC 241b, valve 243b, and nozzle 249b into processing chamber 201. Amine gas also contains C and is also called C, N, and H containing gas.

[0031] As the second N and H-containing gas, for example, a hydrogen nitride-based gas is supplied from the gas supply pipe 232 c through the MFC 241 c , the valve 243 c , and the nozzle 249 c into the processing chamber 201 .

[0032] As a gas containing oxygen (O), for example, a gas containing O and H is supplied from the gas supply pipe 232 d into the processing chamber 201 via the MFC 241 d , the valve 243 d , the gas supply pipe 232 b , and the nozzle 249 b .

[0033] Inert gas is supplied from gas supply pipes 232e to 232g via MFCs 241e to 241g, valves 243e to 243g, gas supply pipes 232a to 232c, and nozzles 249a to 249c into the processing chamber 201. The inert gas functions as a purge gas, carrier gas, dilution gas, and the like.

[0034] The raw gas supply system (silane-based gas supply system) is primarily composed of gas supply pipe 232a, MFC 241a, and valve 243a. The first N- and H-containing gas supply system (amine-based gas supply system) is primarily composed of gas supply pipe 232b, MFC 241b, and valve 243b. The second N- and H-containing gas supply system (nitride-based gas supply system) is primarily composed of gas supply pipe 232c, MFC 241c, and valve 243c. The O-containing gas supply system is primarily composed of gas supply pipe 232d, MFC 241d, and valve 243d. The inert gas supply system is primarily composed of gas supply pipes 232e-232g, MFCs 241e-241g, and valves 243e-243g.

[0035] Any or all of the various supply systems described above may be configured as an integrated supply system 248, which integrates valves 243a-243g, MFCs 241a-241g, and the like. Integrated supply system 248 is connected to gas supply pipes 232a-232g, respectively, and is configured such that the supply of various gases into gas supply pipes 232a-232g, namely, the opening and closing of valves 243a-243g and the flow rate adjustment of MFCs 241a-241g, are controlled by controller 121 (described later). Integrated supply system 248 is composed of a single or split manifold, and can be attached to and detached from gas supply pipes 232a-232g, etc., as a unit. Maintenance, replacement, and expansion of integrated supply system 248 can be performed on a unit basis.

[0036] An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided at the lower side wall of the reaction tube 203. Figure 2As shown, the exhaust port 231a is provided at a position opposite (facing) the nozzles 249a to 249c (gas supply holes 250a to 250c) across the wafer 200 when viewed from above. The exhaust port 231a may also be provided from the lower portion to the upper portion of the side wall of the reaction tube 203, that is, along the wafer arrangement area. The exhaust port 231a is connected to the exhaust pipe 231. The exhaust pipe 231 is connected to a vacuum pump 246 as a vacuum exhaust device via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller; automatic pressure controller) valve 244 as a pressure regulator (pressure regulating unit). The APC valve 244 is configured to open and close the valve while the vacuum pump 246 is in operation, thereby enabling and disabling vacuum exhaust within the processing chamber 201. Furthermore, the valve opening is adjusted based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is in operation, thereby adjusting the pressure within the processing chamber 201. The exhaust system primarily comprises the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may also be included in the exhaust system.

[0037] A sealing cover 219 is provided below the manifold 209. The sealing cover 219 serves as a furnace port cover and can hermetically seal the lower end opening of the manifold 209. The sealing cover 219 is made of a metal material such as SUS and is formed into a disc shape. An O-ring 220b serving as a sealing member that abuts the lower end of the manifold 209 is provided on the upper surface of the sealing cover 219. A rotating mechanism 267 for rotating the wafer boat 217, which will be described later, is provided below the sealing cover 219. The rotating shaft 255 of the rotating mechanism 267 passes through the sealing cover 219 and is connected to the wafer boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217. The sealing cover 219 is configured to be able to be raised and lowered in the vertical direction by the wafer boat elevator 115, which is provided as a lifting mechanism outside the reaction tube 203. The boat elevator 115 serves as a transport device (transport mechanism), and moves the sealing cap 219 upward and downward to carry (transport) the wafers 200 into and out of the processing chamber 201 .

[0038] A gate 219s, serving as a furnace opening cover, is installed below the manifold 209. When the sealing cover 219 is lowered and the wafer boat 217 is removed from the processing chamber 201, the gate 219s hermetically seals the lower opening of the manifold 209. The gate 219s is formed of a metal material, such as SUS, and is disc-shaped. An O-ring 220c, serving as a sealing member, is installed on the top surface of the gate 219s, abutting against the lower end of the manifold 209. The opening and closing movements (lifting, rotation, etc.) of the gate 219s are controlled by the gate opening and closing mechanism 115s.

[0039] The wafer boat 217, serving as a substrate support, is designed to support multiple wafers 200, for example, 25 to 200, aligned vertically in a horizontal position with their centers aligned. The wafer boat 217 is made of a heat-resistant material such as quartz or SiC. A multi-layered insulation plate 218, made of a heat-resistant material such as quartz or SiC, is supported beneath the wafer boat 217. These insulation plates 218 are supported vertically in multiple layers.

[0040] A temperature sensor 263 is provided as a temperature detector within the reaction tube 203. The power supply state of the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, thereby achieving a desired temperature distribution within the processing chamber 201. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0041] like Figure 3 As shown, the control unit (control unit), or controller 121, is comprised of a computer comprising a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with CPU 121a via an internal bus 121e. Controller 121 is connected to an input / output device 122, such as a touch panel.

[0042] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. The storage device 121c stores in a readable manner: a control program for controlling the operation of the substrate processing device, a process recipe that records the order, conditions, etc. of the substrate processing to be described later, etc. The process recipe is combined and formed to function as a program in order for the controller 121 to execute each step in the substrate processing to be described later to obtain a predetermined result. Hereinafter, process recipes, control programs, etc. will also be simply referred to as programs. In addition, process recipes will also be referred to as recipes. In this specification, the meaning of "program" includes: the case of only referring to a recipe alone, the case of only referring to a control program alone, or both cases. RAM121b is configured as a storage area (work area) and temporarily holds the programs, data, etc. read by CPU121a.

[0043] 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, gate opening and closing mechanism 115s, etc.

[0044] The CPU 121a reads and executes a control program from the storage device 121c, and is configured to read a recipe from the storage device 121c based on an operation command or the like input from the input / output device 122. In accordance with the contents of the read recipe, the CPU 121a controls: flow rate adjustment of various gases by the MFCs 241a to 241g; opening and closing of the valves 243a to 243g; opening and closing of the APC valve 244 and pressure adjustment of the APC valve 244 by the pressure sensor 245; starting and stopping of the vacuum pump 246; temperature adjustment of the heater 207 by the temperature sensor 263; rotation and rotation speed adjustment of the wafer boat 217 by the rotation mechanism 267; raising and lowering of the wafer boat 217 by the wafer elevator 115; and opening and closing of the gate 219s by the gate opening and closing mechanism 115s.

[0045] The controller 121 can be constructed 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, an optical magnetic 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 composed of a storage medium that can be accessed by a computer. Hereinafter, these simple titles will also be collectively referred to as storage media. When "storage medium" is mentioned in this specification, it includes: the case of referring to only the storage device 121c alone, the case of referring to only the external storage device 123 alone, or both cases. In addition, the provision of the program to the computer can also be carried out without using the external storage device 123, but by using a communication method such as the Internet or a dedicated line.

[0046] (2) Substrate processing

[0047] Mainly refer to Figure 4 As one of the manufacturing processes for semiconductor devices, an example processing sequence for forming a film on the surface of a substrate, wafer 200, using the aforementioned substrate processing apparatus will be described. Furthermore, this embodiment will describe an example of a silicon substrate (silicon wafer) having recessed portions, such as grooves and holes, formed on its surface, serving as wafer 200. In the following description, the operations of the various components of the substrate processing apparatus are controlled by controller 121.

[0048] like Figure 4 As shown, in the processing sequence of this method, the following are executed:

[0049] The cycle includes: a step of supplying a raw material gas to the wafer 200 having recessed portions formed on the surface thereof (raw material gas supply), a step of supplying a first N- and H-containing gas to the wafer 200 (first N- and H-containing gas supply), and a step of supplying a second N- and H-containing gas to the wafer 200 (second N- and H-containing gas supply), wherein the cycle is performed a predetermined number of times (n times, where n is an integer greater than or equal to 1) at a first temperature, thereby causing oligomers containing at least one element contained in the raw material gas, the first N- and H-containing gas, and the second N- and H-containing gas to generate, grow, and flow on the surface and in the recessed portions of the wafer 200, thereby forming an oligomer-containing layer on the surface and in the recessed portions of the wafer 200 (forming an oligomer-containing layer); and

[0050] For the wafer 200 having an oligomer-containing layer formed on the surface and in the recessed portion of the wafer 200, a post-processing (hereinafter also referred to as PT) is performed at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface and in the recessed portion of the wafer 200, and forming a film formed by the modified oligomer-containing layer in a manner embedded in the recessed portion (PT).

[0051] In addition, Figure 4 In the processing sequence shown, the supply of the raw material gas, the supply of the first N, H-containing gas, and the supply of the second N, H-containing gas are not performed simultaneously.

[0052] In this specification, for convenience, the above-mentioned processing sequence is also represented as follows. The same reference numerals are also used in the following description of modifications including the second and third embodiments.

[0053] (raw material gas → first nitrogen- and hydrogen-containing gas → second nitrogen- and hydrogen-containing gas) × n → PT

[0054] In this specification, the term "wafer" includes the following: the wafer itself; the wafer and a stack of predetermined layers or films formed on its surface. The term "surface of a wafer" includes the surface of the wafer itself; the surface of a predetermined layer formed on the wafer. The term "forming a predetermined layer on a wafer" includes the formation of a predetermined layer directly on the surface of the wafer itself; and the formation of a predetermined layer on top of a layer formed on the wafer. The term "substrate" also has the same meaning as "wafer" in this specification.

[0055] (Wafer loading and wafer boat introduction)

[0056] After a plurality of wafers 200 are loaded into the wafer boat 217 (wafer loading), the gate opening and closing mechanism 115s is used to move the gate 219s to open the lower end opening of the manifold 209 (gate opening). Figure 1As shown, the boat 217 supporting a plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat introduction). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.

[0057] (Pressure adjustment and temperature adjustment)

[0058] After the wafer boat is introduced, in order to make the space in the processing chamber 201, that is, the space where the wafer 200 is located, reach the required pressure (vacuum degree), the vacuum pump 246 is used to perform vacuum exhaust (decompression exhaust). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback controlled (pressure adjusted) based on the measured pressure information. In addition, in order to make the wafer 200 in the processing chamber 201 reach the required processing temperature, the heater 207 is used to heat it. At this time, in order to make the temperature distribution in the processing chamber 201 reach the required temperature, the power state of the heater 207 is feedback controlled (temperature adjusted) based on the temperature information detected by the temperature sensor 263. In addition, the rotation mechanism 267 is used to start rotating the wafer 200. The exhaust in the processing chamber 201, the heating and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.

[0059] (Formation of Oligomer-Containing Layer)

[0060] Then, execute the following steps 1 to 3 in sequence.

[0061] [Step 1]

[0062] In this step, a source gas is supplied to the wafer 200 in the processing chamber 201 .

[0063] Specifically, valve 243a is opened to allow the raw material gas to flow into gas supply pipe 232a. The raw material gas is flow-regulated by MFC 241a, supplied into processing chamber 201 through nozzle 249a, and exhausted from exhaust port 231a. At this point, the raw material gas is supplied to wafer 200 (raw material gas supply). At this point, valves 243e to 243g are opened to allow inert gas to be supplied into processing chamber 201 through nozzles 249a to 249c, respectively.

[0064] After a predetermined period of time has passed, valve 243a is closed, stopping the supply of raw material gas into processing chamber 201. Furthermore, processing chamber 201 is evacuated to remove any remaining gas and the like. At this point, valves 243e to 243g are opened, and inert gas is supplied into processing chamber 201 via nozzles 249a to 249c. The inert gas supplied through nozzles 249a to 249c acts as a purge gas, thereby purging the space within processing chamber 201, where wafers 200 are located.

[0065] As the raw material gas, silane gases containing no carbon or halogen such as monosilane (SiH4, abbreviated as: MS) gas and disilane (Si2H6, abbreviated as: DS) gas, halogen silane gases containing no carbon such as dichlorosilane (SiH2Cl2, abbreviated as: DCS) gas and hexachlorodisilane (Si2Cl6, abbreviated as: HCDS) gas, alkylsilane 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, bis(trichlorosilyl)methane ((SiCl3)2CH2, abbreviated as: BTCSM) gas, 1,2 - Alkylene halosilane gases such as bis(trichlorosilyl)ethane ((SiCl3)2C2H4, abbreviated as BTCSE) gas, 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.

[0066] As the inert gas, a rare gas such as nitrogen (N 2 ), argon (Ar), helium (He), neon (Ne), or xenon (Xe) can be used. This also applies to the steps described below.

[0067] [Step 2]

[0068] In this step, a first N and H containing gas is supplied to the wafer 200 in the processing chamber 201 .

[0069] Specifically, valve 243b is opened to allow the first N- and H-containing gas to flow into gas supply pipe 232b. The flow rate of the first N- and H-containing gas is adjusted by MFC 241b, supplied into processing chamber 201 via nozzle 249b, and exhausted from exhaust port 231a. At this point, the first N- and H-containing gas is supplied to wafer 200 (supplying the first N- and H-containing gas). At this point, valves 243e to 243g can be opened to supply inert gas into processing chamber 201 via nozzles 249a to 249c, respectively.

[0070] After a predetermined time has passed, valve 243b is closed to stop supplying the first N, H-containing gas into process chamber 201. Residual gas in process chamber 201 is then purged from process chamber 201 using the same process sequence and conditions as in step 1.

[0071] As the first N and H-containing gas, for example, nitride-based gases such as ammonia (NH3), ethylamine-based 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-based gases such as monomethylamine (CH3NH2, abbreviated as: MMA) gas, dimethylamine ((CH3)2NH, abbreviated as: DMA) gas, and trimethylamine ((CH3)3N, abbreviated as: TMA) gas, organic hydrazine-based gases such as monomethylhydrazine ((CH3)HN2H2, abbreviated as: MMH) gas, dimethylhydrazine ((CH3)2N2H2, abbreviated as: DMH) gas, and trimethylhydrazine ((CH3)2N2(CH3)H, abbreviated as: TMH) gas, pyridine (C5H5N) gas, and piperazine (C4H 10 N2) gas and other cyclic amine gases.

[0072] [Step 3]

[0073] In this step, the second N and H containing gas is supplied to the wafer 200 in the processing chamber 201 .

[0074] Specifically, valve 243c is opened to allow the second N- and H-containing gas to flow into gas supply pipe 232c. The second N- and H-containing gas is flow-regulated by MFC 241c, supplied into processing chamber 201 via nozzle 249c, and exhausted from exhaust port 231a. At this point, the second N- and H-containing gas is supplied to wafer 200 (supplying the second N- and H-containing gas). At this point, valves 243e to 243g can be opened to supply inert gas into processing chamber 201 via nozzles 249a to 249c, respectively.

[0075] After a predetermined time has passed, valve 243c is closed to stop supplying the second N, H-containing gas into process chamber 201. Residual gas in process chamber 201 is then purged from process chamber 201 using the same process sequence and conditions as in step 1.

[0076] As the second N- and H-containing gas, for example, ammonia (NH₃), hydrazine (N₂H₂), hydrazine (N₂H₄), or N₃H₄ gas, a nitride-based gas can be used. The second N- and H-containing gas is preferably a gas with a different molecular structure from the first N- and H-containing gas. However, depending on the processing conditions, a gas with the same molecular structure as the first N- and H-containing gas may also be used.

[0077] [Scheduled number of implementations]

[0078] Thereafter, the loop in which the above steps 1 to 3 are performed non-simultaneously, that is, asynchronously, is executed a predetermined number of times (n times, where n is an integer equal to or greater than 1).

[0079] At this time, if the raw material gas exists alone, the cycle is performed a predetermined number of times under conditions (temperatures) where physical adsorption of the raw material gas occurs predominantly compared to chemical adsorption of the raw material gas. Preferably, if the raw material gas exists alone, the cycle is performed a predetermined number of times under conditions (temperatures) where physical adsorption of the raw material gas occurs predominantly compared to thermal decomposition of the raw material gas and chemical adsorption of the raw material gas. Preferably, if the raw material gas exists alone, the cycle is performed a predetermined number of times under conditions (temperatures) where the raw material gas does not thermally decompose and physical adsorption of the raw material gas occurs predominantly compared to chemical adsorption of the raw material gas. Preferably, the cycle is performed a predetermined number of times under conditions (temperatures) where the oligomer-containing layer exhibits fluidity. Preferably, the cycle is performed a predetermined number of times under conditions (temperatures) where the oligomer-containing layer flows deep into a recess formed on the surface of the wafer 200 and fills the recess from deep within the recess with the oligomer-containing layer.

[0080] The following are examples of processing conditions for the supply of raw material gases:

[0081] Raw material gas supply flow rate: 10~1000sccm;

[0082] Raw gas supply time: 1 to 300 seconds;

[0083] Inert gas supply flow rate (corresponding to the gas supply pipe): 10 to 10,000 sccm;

[0084] Treatment temperature (first temperature): 0-150°C, preferably 10-100°C, more preferably 20-60°C;

[0085] Treatment pressure: 10-6000 Pa, preferably 50-2000 Pa.

[0086] In this specification, when a numerical range is indicated as "0 to 150°C," the range includes both the lower and upper limits. Therefore, for example, "0 to 150°C" means "0°C to 150°C." The same applies to other numerical ranges.

[0087] The following are examples of the processing conditions for supplying the first N and H-containing gas:

[0088] First N and H-containing gas supply flow rate: 10-5000 sccm;

[0089] First N and H-containing gas supply time: 1 to 300 seconds.

[0090] Other processing conditions may be the same as those for the raw material gas supply.

[0091] The following are examples of the processing conditions for supplying the second N and H-containing gas:

[0092] Second N and H-containing gas supply flow rate: 10-5000 sccm;

[0093] Second N and H-containing gas supply time: 1 to 300 seconds.

[0094] Other processing conditions may be the same as those for the raw material gas supply.

[0095] By carrying out the following processing conditions under which the raw material gas is supplied, the first N- and H-containing gas is supplied, and the second N- and H-containing gas is supplied, oligomers containing at least one element contained in the raw material gas, the first N- and H-containing gas, and the second N- and H-containing gas can be generated, grown, and flowed on the surface and in the recesses of the wafer 200, thereby forming an oligomer-containing layer on the surface and in the recesses of the wafer 200. In addition, an oligomer refers to a polymer with a relatively low molecular weight (for example, a molecular weight of 10,000 or less) formed by the combination of a relatively small number of monomers (for example, 10 to 100). When alkyl halosilane gases such as alkylchlorosilane gases, amine gases, and hydrogen nitride gases are used as the raw material gas, the first N- and H-containing gas, and the second N- and H-containing gas, respectively, the oligomer-containing layer contains, for example, various elements such as Si, Cl, and N, or can be composed of C x H 2x+1 A layer of a substance represented by the chemical formula (x is an integer of 1 to 3).

[0096] Furthermore, if the processing temperature is below 0°C, the raw material gas supplied into the processing chamber 201 is likely to liquefy, making it difficult to supply the raw material gas in a gaseous state to the wafer 200. In this case, the reaction to form the oligomer-containing layer described above may be difficult to proceed, and the oligomer-containing layer may be difficult to form on the surface and within the recesses of the wafer 200. This problem can be solved by setting the processing temperature above 0°C. Setting the processing temperature above 10°C can fully solve this problem, and setting the processing temperature above 20°C can even more fully solve this problem.

[0097] Furthermore, if the processing temperature exceeds 150°C, the catalytic effect of the first N and H-containing gas, described later, will weaken, potentially hindering the reaction to form the oligomer-containing layer. In this case, oligomers generated on the surface and within the recesses of wafer 200 are more likely to detach than to grow, potentially hindering the formation of the oligomer-containing layer on the surface and within the recesses of wafer 200. This problem can be resolved by setting the processing temperature below 150°C. Setting the processing temperature below 100°C fully resolves this issue, and setting the processing temperature below 60°C even more fully resolves it.

[0098] Therefore, the treatment temperature is set to 0°C to 150°C, preferably 10°C to 100°C, and more preferably 20°C to 60°C.

[0099] In addition, the following are examples of the treatment conditions for purging:

[0100] Inert gas supply flow rate (corresponding to the gas supply pipe): 10-20000 sccm;

[0101] Inert gas supply time: 1 to 300 seconds;

[0102] Processing pressure: 10~6000Pa.

[0103] Other processing conditions may be the same as those for the raw material gas supply.

[0104] By performing the purge under the above-described processing conditions, the flow of the oligomer-containing layer formed on the surface of the wafer 200 and in the recesses can be promoted, and excess components contained in the oligomer-containing layer, such as excess gas and byproducts containing Cl, can be discharged.

[0105] (Post-processing)

[0106] After the oligomer-containing layer is formed on the surface of the wafer 200 and in the recess, the output of the heater 207 is adjusted to change the temperature of the wafer 200 to a second temperature higher than the first temperature, preferably higher than the first temperature.

[0107] At this time, an inert gas, such as N₂ gas, is supplied to the wafers 200 in the processing chamber 201. Specifically, valves 243e-243g are opened to allow the inert gas to flow through the gas supply pipes 232e-232g. The inert gas is flow-controlled by MFCs 241e-241g, supplied into the processing chamber 201 through nozzles 249a-249c, and exhausted from exhaust port 231a. At this time, the inert gas is supplied to the wafers 200.

[0108] This step is preferably performed under conditions that allow the oligomer-containing layer formed on the surface and in the recesses of the wafer 200 to develop fluidity. Furthermore, this step is preferably performed under conditions that promote the fluidity of the oligomer-containing layer formed on the surface and in the recesses of the wafer 200 and discharge excess components contained in the oligomer-containing layer, such as excess gas and Cl-containing byproducts, thereby densifying the oligomer-containing layer.

[0109] The following are examples of post-processing conditions:

[0110] Inert gas supply flow rate (corresponding to the gas supply pipe): 10-20000 sccm;

[0111] Treatment temperature (second temperature): 100-1000°C, preferably 200-600°C;

[0112] Processing pressure: 10-80000Pa, preferably 200-6000Pa;

[0113] Processing time: 300 to 10,800 seconds.

[0114] By performing post-treatment under the above-described conditions, the oligomer-containing layer formed on the surface and within the recesses of wafer 200 can be modified. This allows a silicon carbonitride film (SiCN film) containing Si, C, and N to be formed within the recesses as a modified oligomer-containing layer. Furthermore, the flow of the oligomer-containing layer can be promoted, and excess components in the oligomer-containing layer can be discharged, resulting in a densified oligomer-containing layer.

[0115] (Post-purge and atmospheric pressure recovery)

[0116] After the SiCN film is formed, an inert gas is supplied from nozzles 249a to 249c as a purge gas into the processing chamber 201, and the gas is exhausted from exhaust port 231a. This purges the processing chamber 201, removing any remaining gas and reaction byproducts (post-purge). The atmosphere in the processing chamber 201 is then replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (return to atmospheric pressure).

[0117] (Wafer boat export and wafer unloading)

[0118] The sealing cap 219 is then lowered by the boat elevator 115, opening the lower end of the manifold 209. The processed wafers 200, supported by the boat 217, are then unloaded from the lower end of the manifold 209 to the exterior of the reaction tube 203 (boat unloading). After the boat is unloaded, the gate 219s is moved, sealing the lower end opening of the manifold 209 via the O-ring 220c (gate closing). The processed wafers 200 are unloaded from the boat 217 (wafer unloading).

[0119] (3) Effects of this method

[0120] According to this aspect, one or more of the following effects can be obtained.

[0121] (a) By forming the oligomer-containing layer at the first temperature and performing post-treatment at a second temperature higher than the first temperature, the embedding characteristics of the film formed in the recess can be improved. Furthermore, by performing post-treatment at the second temperature higher than the first temperature, the above-mentioned effect can be further enhanced.

[0122] (b) When forming a layer containing oligomers, if the raw material gas exists alone, the cycle is performed a predetermined number of times under conditions where physical adsorption of the raw material gas mainly occurs compared to chemical adsorption of the raw material gas, thereby improving the fluidity of the oligomer-containing layer and improving the embedding characteristics of the film formed in the recess.

[0123] (c) When forming the oligomer-containing layer, if the raw material gas is present alone, the flowability of the oligomer-containing layer can be improved by performing a predetermined number of cycles under conditions in which physical adsorption of the raw material gas occurs primarily, rather than thermal decomposition and chemical adsorption of the raw material gas. As a result, the embedding characteristics of the film formed in the recess can be improved.

[0124] (d) When forming the oligomer-containing layer, if the raw material gas is present alone, the fluidity of the oligomer-containing layer can be improved by circulating the raw material gas a predetermined number of times under conditions where the raw material gas does not undergo thermal decomposition and physical adsorption of the raw material gas occurs predominantly, rather than chemical adsorption. As a result, the embedding characteristics of the film formed within the recess can be improved.

[0125] (e) When forming the oligomer-containing layer, the embedding property of the film formed in the concave portion can be improved by performing the cycle a predetermined number of times under the condition that the oligomer-containing layer develops fluidity.

[0126] (f) When forming the oligomer-containing layer, the oligomer-containing layer is caused to flow deep into the recess, and the cycle is performed a predetermined number of times under the condition that the recess is filled from deep inside the recess with the oligomer-containing layer, thereby improving the embedding characteristics of the film formed in the recess.

[0127] (g) By using an alkylchlorosilane gas as a raw material gas, the oligomer-containing layer can contain Si, C, and Cl.

[0128] (h) By making the molecular structures of the first N- and H-containing gas different from those of the second N- and H-containing gas, the gases can have different functions. For example, by using an amine gas as the first N- and H-containing gas, as in this embodiment, the gas can function as a catalyst, activating the source gas physically adsorbed on the surface of wafer 200 by the supply of the source gas. Alternatively, by using a hydrogen nitride gas as the second N- and H-containing gas, the gas can function as an N source, thereby adding N to the oligomer-containing layer.

[0129] (i) When forming the oligomer-containing layer, a cycle in which the raw material gas supply, the first N / H-containing gas supply, and the second N / H-containing gas supply are performed non-simultaneously is performed a predetermined number of times, thereby improving the embedding characteristics of the film formed in the recess.

[0130] This is believed to be due to the following reason: the raw material gas and the first N- and H-containing gas acting as a catalyst are supplied at different times, thereby controlling the deviation in the mixing state of the raw material gas and the first N- and H-containing gas. According to this method, the growth deviation of the oligomers generated at multiple locations on the surface of wafer 200 and within the recesses can be improved, and the growth deviation in small areas can be suppressed, thereby suppressing voids or seams within the recesses caused by such deviations. As a result, the embedding characteristics of the film formed in the recesses can be improved. In other words, void-free and seam-free embedding can be achieved.

[0131] (j) By performing a purge at a predetermined timing during formation of the oligomer-containing layer, the embedding characteristics of the film formed within the recess can be improved. Furthermore, the impurity concentration of the film formed so as to embed within the recess can be reduced. Consequently, the wet etching resistance of the film formed within the recess can be improved.

[0132] (k) By performing post-treatment under conditions that allow the oligomer-containing layer to develop fluidity, the embedding characteristics of the film formed in the recessed portion can be improved.

[0133] (1) During post-processing, the flow of the oligomer-containing layer is promoted, and excess components contained in the oligomer-containing layer are discharged, thereby densifying the oligomer-containing layer. This improves the embedding characteristics of the film formed in the recess. Furthermore, the impurity concentration of the film formed by embedding in the recess can be reduced, and the film density can be increased. This improves the wet etching resistance of the film formed in the recess.

[0134] (m) Supplying N-containing gas to wafer 200 during post-processing can promote the flow of the oligomer-containing layer, thereby improving the embedding characteristics of the film formed within the recess. Furthermore, the impurity concentration of the film formed by embedding within the recess can be reduced, thereby increasing the film density. Consequently, the wet etching resistance of the film formed within the recess can be improved.

[0135] (N) The aforementioned effects can also be achieved when the various raw material gases, various first N- and H-containing gases, various second N- and H-containing gases, and various inert gases described above are used to form the oligomer-containing layer. Furthermore, the aforementioned effects can also be achieved when the order of gas supply during the cycle is changed. Furthermore, the aforementioned effects can also be achieved when a gas other than the N-containing gas is used in post-processing.

[0136] <Second aspect of the present disclosure>

[0137] Next, the main reference Figure 5 The second embodiment of the present disclosure will be described.

[0138] In accordance with Figure 5 When forming the oligomer-containing layer using the following processing sequence, the following cycle may be performed a predetermined number of times (n times, where n is an integer greater than or equal to 1), and the cycles may be performed non-simultaneously:

[0139] Simultaneously performing the steps of supplying a raw material gas to the wafer 200 and supplying a first N and H-containing gas to the wafer 200; and

[0140] A step of supplying a second N and H containing gas to the wafer 200 .

[0141] (raw material gas + first nitrogen- and hydrogen-containing gas → second nitrogen- and hydrogen-containing gas) × n → PT

[0142] This method can also achieve the same effects as the first method described above. In addition, this method can increase the circulation rate by simultaneously supplying the raw material gas and the first N and H-containing gas, thereby improving the productivity of substrate processing.

[0143] <Third Aspect of the Present Disclosure>

[0144] Next, the main reference Figure 6 A third embodiment of the present disclosure will be described.

[0145] In accordance with Figure 6 When forming the oligomer-containing layer using the following processing sequence, the following cycle may be performed a predetermined number of times (n times, where n is an integer greater than or equal to 1), and the cycles may be performed non-simultaneously:

[0146] A step of simultaneously supplying a raw material gas to the wafer 200 and a step of supplying a first N and H-containing gas to the wafer 200;

[0147] supplying a second N and H containing gas to the wafer 200; and

[0148] A step of supplying a first N and H containing gas to the wafer 200 .

[0149] (raw material gas + first N, H-containing gas → second N, H-containing gas → first N, H-containing gas) × n → PT

[0150] This method can also achieve the same effects as the first method described above. Furthermore, in this method, the first N- and H-containing gas circulated during the first cycle can function as a catalyst to activate the raw material gas. Furthermore, the second N- and H-containing gas circulated during the second cycle can function as a reactive purge gas, removing byproducts generated during the formation of the oligomer-containing layer. The processing conditions for supplying these first N- and H-containing gases can be the same as those for supplying the first N- and H-containing gas described above.

[0151] <Other aspects of the present disclosure>

[0152] Although various aspects of the present disclosure have been specifically described above, the present disclosure is not limited to the above aspects and various modifications can be made without departing from the spirit and scope of the present disclosure.

[0153] For example, in post-processing, an H-containing gas such as hydrogen (H2), an N-containing gas such as NH3, i.e., a gas containing N and H, may be supplied to the wafer 200 on which the oligomer-containing layer has been formed. An O-containing gas such as H2O, i.e., a gas containing O and H, may be supplied. Furthermore, O2 gas may be supplied as an O-containing gas. Specifically, in post-processing, at least one of an N-containing gas, an H-containing gas, an N and H-containing gas, an O-containing gas, and a gas containing O and H may be supplied to the wafer 200 on which the oligomer-containing layer has been formed.

[0154] The following are examples of treatment conditions when supplying H-containing gas in post-treatment:

[0155] H-containing gas supply flow rate: 10-3000 sccm;

[0156] Treatment temperature (second temperature): 100-1000°C, preferably 200-600°C;

[0157] Processing pressure: 10-1000 Pa, preferably 200-800 Pa;

[0158] Processing time: 300 to 10,800 seconds.

[0159] The following are examples of treatment conditions when supplying N and H containing gas in post-treatment:

[0160] N and H containing gas supply flow rate: 10~10000sccm;

[0161] Treatment temperature (second temperature): 100-1000°C, preferably 200-600°C;

[0162] Processing pressure: 10-6000Pa, preferably 200-2000Pa;

[0163] Processing time: 300 to 10,800 seconds.

[0164] The following are examples of treatment conditions when supplying an O-containing gas in post-treatment:

[0165] O-containing gas supply flow rate: 10-10000 sccm;

[0166] Treatment temperature (second temperature): 100-1000°C, preferably 100-600°C;

[0167] Processing pressure: 10-90000Pa, preferably 20000-80000Pa;

[0168] Processing time: 300 to 10,800 seconds.

[0169] In these cases as well, the same effects as those of the first embodiment described above can be obtained.

[0170] Furthermore, when post-treatment is performed in an atmosphere containing H or N and H gases, the fluidity of the oligomer-containing layer can be improved, and the embedding characteristics of the film formed within the recessed portion can be improved, compared to when post-treatment is performed in an inert gas atmosphere such as N2 gas. Furthermore, when post-treatment is performed in an atmosphere containing H or N and H gases, the impurity concentration of the film formed within the recessed portion can be reduced, the film density can be increased, and the wet etching resistance can be improved, compared to when post-treatment is performed in an inert gas atmosphere such as N2 gas. Furthermore, when post-treatment is performed in an atmosphere containing N and H gases, these effects can be enhanced compared to when post-treatment is performed in an atmosphere containing H gas.

[0171] Furthermore, when post-treatment is performed in an O-containing gas atmosphere, the film obtained by modifying the oligomer-containing layer can contain O, thereby converting the film into a silicon oxynitride carbon film (SiOCN film) containing Si, O, C, and N.

[0172] And for example in post-processing it can be done non-simultaneously:

[0173] a step of supplying at least one of N-containing gas such as N 2 gas, H-containing gas such as H 2 gas, and N- and H-containing gas such as NH 3 gas to the wafer 200 on which the oligomer-containing layer is formed; and

[0174] A step of supplying an O-containing gas (O and H-containing gas) such as H 2 O gas to the wafer 200 on which the oligomer-containing layer is formed.

[0175] At this time, in the above two steps, the former step can be called the first post-processing, and the latter step can be called the second post-processing.

[0176] The processing conditions of each of the first and second post-processing can be the same as the processing conditions of the post-processing in each of the above-mentioned forms.

[0177] In this case as well, the same effects as those of the first embodiment described above can be obtained.

[0178] Furthermore, when post-treatment is performed in an O-containing gas atmosphere, O can be incorporated into the film formed by modifying the oligomer-containing layer, thereby converting the film into a SiOCN film. Furthermore, by using an O- and H-containing gas such as H2O gas, which has low oxidizing power, as the O-containing gas, the removal of C from the SiOCN film formed by modifying the oligomer-containing layer can be suppressed. Furthermore, by performing the first and second post-treatments in this order, the removal of C from the SiOCN film formed by modifying the oligomer-containing layer can be suppressed.

[0179] Furthermore, for example, the first embodiment and part of the third embodiment may be combined according to the processing sequence shown below.

[0180] (raw material gas → first nitrogen- and hydrogen-containing gas → second nitrogen- and hydrogen-containing gas → first nitrogen- and hydrogen-containing gas) × n → PT

[0181] That is, when forming the oligomer-containing layer, the following cycle may be performed a predetermined number of times (n times, where n is an integer greater than or equal to 1), and the cycles may be performed non-simultaneously:

[0182] a step of supplying a raw material gas to the wafer 200;

[0183] supplying a first N and H containing gas to the wafer 200;

[0184] supplying a second N and H containing gas to the wafer 200; and

[0185] A step of supplying a first N and H containing gas to the wafer 200 .

[0186] According to this processing sequence, it is possible to obtain both the effect obtained by the first aspect and the effect obtained by part of the third aspect.

[0187] In the above-mentioned manner, an example is described in which the formation of the oligomer-containing layer and the post-processing are performed in the same processing chamber 201 (in-situ). However, the present disclosure is not limited to these manners. For example, the formation of the oligomer-containing layer and the post-processing can also be performed in different processing chambers (ex-situ). In this case, the same effect as that of the above-mentioned manner can be obtained. In the above-mentioned various cases, if these steps are performed in-situ, it is possible to avoid the wafer 200 being exposed to the atmosphere during the process, and the wafer 200 can be consistently subjected to these processes under vacuum, so that stable substrate processing can be performed. In addition, if these steps are performed ex-situ, the temperature in each processing chamber can be pre-set to, for example, the processing temperature in each step or a temperature close thereto, which can shorten the time required for temperature adjustment and improve production efficiency.

[0188] While the above description describes an example of forming SiCN and SiOCN films by embedding them in recesses formed on the surface of wafer 200, the present disclosure is not limited to these examples. Specifically, the present disclosure can also be applied to cases where a silicon nitride film (SiN film), a silicon oxide film (SiO film), a silicon oxycarbide film (SiOC film), or a silicon film (Si film) is formed by arbitrarily combining the source gas, the first N- and H-containing gas, and the second N- and H-containing gas, and embedding them in recesses formed on the surface of wafer 200. In these cases, the same effects as those of the above-described method can be achieved.

[0189] Recipes used in substrate processing are preferably prepared separately according to the processing content and pre-stored in the storage device 121c via electronic communication lines or external storage device 123. Furthermore, when processing begins, the CPU 121a preferably selects an appropriate recipe from the multiple recipes stored in the storage device 121c, corresponding to the substrate processing content. This allows a single substrate processing apparatus to reproducibly form films of various film types, composition ratios, film qualities, and film thicknesses. This also reduces the burden on operators, prevents operational errors, and allows for a prompt start of processing.

[0190] The above-mentioned recipes are not limited to newly generated ones; for example, they can also be prepared by modifying an existing recipe installed in a substrate processing apparatus. When modifying a recipe, the modified recipe can be installed in the substrate processing apparatus via an electronic communication line or a storage medium storing the recipe. Alternatively, the input / output device 122 of an existing substrate processing apparatus can be used to directly modify an existing recipe installed in the apparatus.

[0191] The above-described method describes an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at a time. The present disclosure is not limited to the above-described method and can also be advantageously applied to forming a film using a single-wafer-type substrate processing apparatus that processes one or more substrates at a time. Furthermore, the above-described method describes an example of forming a film using a substrate processing apparatus with a hot-wall processing furnace. The present disclosure is not limited to the above-described method and can also be advantageously applied to forming a film using a substrate processing apparatus with a cold-wall processing furnace.

[0192] When these substrate processing apparatuses are used, film formation can be performed with the same timing and processing conditions as those of the above-mentioned embodiment and modified examples, and the same effects as those can be obtained.

[0193] In addition, the above-mentioned embodiments, modifications, etc. may be appropriately combined and applied. The processing sequence and processing conditions in this case may be the same as those of the above-mentioned embodiment, for example.

[0194] Explanation of symbols

[0195] 200—Wafer (substrate); 201—Processing chamber.

Claims

1. A substrate processing method, characterized in that: have: (a) performing a cycle comprising simultaneously supplying a raw material gas to a substrate having a recessed portion formed on its surface, supplying a first nitrogen and hydrogen-containing gas to the substrate, and supplying a second nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers containing an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recessed portion, thereby forming an oligomer-containing layer on the surface of the substrate and in the recessed portion; and (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recess.

2. A substrate processing method, characterized in that: have: (a) performing a cycle comprising simultaneously supplying a raw material gas to a substrate having a recessed portion formed on its surface, supplying a first nitrogen and hydrogen-containing gas to the substrate, supplying a second nitrogen and hydrogen-containing gas to the substrate, and supplying the first nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers containing an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recessed portion, thereby forming an oligomer-containing layer on the surface of the substrate and in the recessed portion; and (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recess.

3. A substrate processing method, characterized in that: have: (a) a step of performing a cycle comprising a step of supplying a raw material gas containing silicon and halogen to a substrate having a recess formed on its surface, a step of supplying a first nitrogen and hydrogen-containing gas to the substrate, and a step of supplying a second nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers of an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recess, thereby forming an oligomer-containing layer on the surface of the substrate and in the recess; and (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recess.

4. A substrate processing method, characterized in that: have: (a) a step of performing a cycle comprising a step of supplying a raw material gas to a substrate having a recessed portion formed on its surface, a step of supplying a first nitrogen and hydrogen-containing gas to the substrate, and a step of supplying a second nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers containing an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recessed portion, thereby forming an oligomer-containing layer on the surface of the substrate and in the recessed portion; and (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film of the modified oligomer-containing layer so as to be embedded in the recess; (b) include: a step of supplying at least one of a nitrogen-containing gas, a hydrogen-containing gas, and a nitrogen-and-hydrogen-containing gas to the substrate; and a step of supplying an oxygen-containing gas to the substrate.

5. The substrate processing method according to any one of claims 1 to 4, characterized in that: In (a), in the presence of the raw material gas alone, the cycle is performed a predetermined number of times under conditions where physical adsorption of the raw material gas occurs predominantly rather than chemical adsorption of the raw material gas.

6. The substrate processing method according to any one of claims 1 to 4, characterized in that: In (a), when the raw material gas exists alone, Under conditions where physical adsorption of the raw material gas occurs predominantly compared to thermal decomposition of the raw material gas and chemical adsorption of the raw material gas, or Under the conditions that the raw material gas does not undergo pyrolysis and physical adsorption of the raw material gas occurs mainly compared to chemical adsorption of the raw material gas, The cycle is performed a predetermined number of times.

7. The substrate processing method according to any one of claims 1 to 4, characterized in that: In (a), the cycle is performed a predetermined number of times under conditions that allow the oligomer-containing layer to develop fluidity.

8. The substrate processing method according to any one of claims 1 to 4, characterized in that: In (a), the cycle is performed a predetermined number of times under the conditions that the oligomer-containing layer flows and flows deep into the recessed portion and the oligomer-containing layer fills the recessed portion from the deep inside the recessed portion.

9. The substrate processing method according to claim 3 or 4, characterized in that: The cycles in (a) are performed non-simultaneously: supplying the raw material gas to the substrate; supplying the first nitrogen and hydrogen-containing gas to the substrate; and a step of supplying the second nitrogen and hydrogen-containing gas to the substrate.

10. The substrate processing method according to any one of claims 1 to 4, characterized in that: The cycle in (a) further includes a step of purging the space where the substrate is located. The purge is used to promote the flow of the oligomer-containing layer and to discharge the remaining components contained in the oligomer-containing layer.

11. The substrate processing method according to any one of claims 1 to 4, characterized in that: In (b), the post-treatment is performed under conditions that allow the oligomer-containing layer to develop fluidity.

12. The substrate processing method according to any one of claims 1 to 4, characterized in that: In (b), the flow of the oligomer-containing layer is promoted, and excess components contained in the oligomer-containing layer are discharged, thereby densifying the oligomer-containing layer.

13. The substrate processing method according to any one of claims 1 to 4, characterized in that: The raw material gas contains silicon, carbon and halogen.

14. The substrate processing method according to any one of claims 1 to 4, characterized in that: The first nitrogen and hydrogen containing gas and the second nitrogen and hydrogen containing gas have different molecular structures.

15. The substrate processing method according to any one of claims 1 to 4, characterized in that: The first nitrogen and hydrogen-containing gas is an amine gas, and the second nitrogen and hydrogen-containing gas is a hydrogen nitride gas.

16. The substrate processing method according to any one of claims 1 to 4, characterized in that: In (b), at least one of a nitrogen-containing gas, a hydrogen-containing gas, a nitrogen-and-hydrogen-containing gas, and an oxygen-containing gas is supplied to the substrate.

17. A method for manufacturing a semiconductor device, characterized in that: have: (a) performing a cycle comprising simultaneously supplying a raw material gas to a substrate having a recessed portion formed on its surface, supplying a first nitrogen and hydrogen-containing gas to the substrate, and supplying a second nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers containing an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recessed portion, thereby forming an oligomer-containing layer on the surface of the substrate and in the recessed portion; and (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recess.

18. A method for manufacturing a semiconductor device, characterized in that: have: (a) performing a cycle comprising simultaneously supplying a raw material gas to a substrate having a recessed portion formed on its surface, supplying a first nitrogen and hydrogen-containing gas to the substrate, supplying a second nitrogen and hydrogen-containing gas to the substrate, and supplying the first nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers containing an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recessed portion, thereby forming an oligomer-containing layer on the surface of the substrate and in the recessed portion; and (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recess.

19. A method for manufacturing a semiconductor device, characterized in that: have: (a) a step of performing a cycle comprising a step of supplying a raw material gas containing silicon and halogen to a substrate having a recess formed on its surface, a step of supplying a first nitrogen and hydrogen-containing gas to the substrate, and a step of supplying a second nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers of an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recess, thereby forming an oligomer-containing layer on the surface of the substrate and in the recess; and (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recess.

20. A method for manufacturing a semiconductor device, characterized in that: have: (a) a step of performing a cycle comprising a step of supplying a raw material gas to a substrate having a recessed portion formed on its surface, a step of supplying a first nitrogen and hydrogen-containing gas to the substrate, and a step of supplying a second nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers containing an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recessed portion, thereby forming an oligomer-containing layer on the surface of the substrate and in the recessed portion; and (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film of the modified oligomer-containing layer so as to be embedded in the recess; (b) include: a step of supplying at least one of a nitrogen-containing gas, a hydrogen-containing gas, and a nitrogen-and-hydrogen-containing gas to the substrate; and a step of supplying an oxygen-containing gas to the substrate.

21. A substrate processing device, characterized in that: have: a raw material gas supply system for supplying raw material gas to the substrate; a first nitrogen and hydrogen containing gas supply system for supplying the first nitrogen and hydrogen containing gas to the substrate; a second nitrogen and hydrogen containing gas supply system for supplying a second nitrogen and hydrogen containing gas to the substrate; a heater that heats the substrate; and a control unit capable of controlling the raw material gas supply system, the first nitrogen and hydrogen-containing gas supply system, the second nitrogen and hydrogen-containing gas supply system, and the heater so as to: (a) perform a cycle comprising simultaneously supplying the raw material gas to a substrate having a recess formed on its surface, supplying the first nitrogen and hydrogen-containing gas to the substrate, and supplying the second nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers containing an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recess, thereby forming an oligomer-containing layer on the surface of the substrate and in the recess; and (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recess.

22. A substrate processing device, characterized in that: have: a raw material gas supply system for supplying raw material gas to the substrate; a first nitrogen and hydrogen containing gas supply system for supplying the first nitrogen and hydrogen containing gas to the substrate; a second nitrogen and hydrogen containing gas supply system for supplying a second nitrogen and hydrogen containing gas to the substrate; a heater that heats the substrate; and a control unit capable of controlling the raw material gas supply system, the first nitrogen and hydrogen-containing gas supply system, the second nitrogen and hydrogen-containing gas supply system, and the heater so as to: (a) perform a cycle comprising simultaneously performing a process of supplying the raw material gas to a substrate having a recess formed on a surface thereof, a process of supplying the first nitrogen and hydrogen-containing gas to the substrate, a process of supplying the second nitrogen and hydrogen-containing gas to the substrate, and a process of supplying the first nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers containing an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recess, thereby forming an oligomer-containing layer on the surface of the substrate and in the recess; and (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recess.

23. A substrate processing device, characterized in that: have: a raw material gas supply system for supplying a raw material gas containing silicon and halogen to the substrate; a first nitrogen and hydrogen containing gas supply system for supplying the first nitrogen and hydrogen containing gas to the substrate; a second nitrogen and hydrogen containing gas supply system for supplying a second nitrogen and hydrogen containing gas to the substrate; a heater that heats the substrate; and a control unit capable of controlling the raw material gas supply system, the first nitrogen and hydrogen-containing gas supply system, the second nitrogen and hydrogen-containing gas supply system, and the heater so as to: (a) perform a cycle comprising a process of supplying the raw material gas to a substrate having a recess formed on a surface thereof, a process of supplying the first nitrogen and hydrogen-containing gas to the substrate, and a process of supplying the second nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers containing an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recess, thereby forming an oligomer-containing layer on the surface of the substrate and in the recess; and (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recess.

24. A substrate processing device, characterized in that: have: a raw material gas supply system for supplying raw material gas to the substrate; a first nitrogen and hydrogen containing gas supply system for supplying the first nitrogen and hydrogen containing gas to the substrate; a second nitrogen and hydrogen containing gas supply system for supplying a second nitrogen and hydrogen containing gas to the substrate; a nitrogen and / or hydrogen-containing gas supply system for supplying at least one of nitrogen-containing gas, hydrogen-containing gas, and nitrogen-and-hydrogen-containing gas to the substrate; an oxygen-containing gas supply system for supplying oxygen-containing gas to the substrate; a heater that heats the substrate; and a control unit capable of controlling the raw material gas supply system, the first nitrogen and hydrogen-containing gas supply system, the second nitrogen and hydrogen-containing gas supply system, the nitrogen and / or hydrogen-containing gas supply system, the oxygen-containing gas supply system, and the heater so as to: (a) perform a cycle comprising a process of supplying the raw material gas to a substrate having a recess formed on a surface thereof, a process of supplying the first nitrogen and hydrogen-containing gas to the substrate, and a process of supplying the second nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers of an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recess, thereby forming an oligomer-containing layer on the surface of the substrate and in the recess; and (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner buried in the recess, (b) includes: supplying a nitrogen-containing gas, a hydrogen-containing gas, and at least one of nitrogen- and hydrogen-containing gases to the substrate; and supplying an oxygen-containing gas to the substrate.

25. A program product, characterized in that The computer enables the substrate processing device to execute: (a) performing a cycle comprising the steps of simultaneously supplying a raw material gas to a substrate having a recessed portion formed on its surface, supplying a first nitrogen and hydrogen-containing gas to the substrate, and supplying a second nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers containing an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recessed portion, thereby forming an oligomer-containing layer on the surface of the substrate and in the recessed portion; as well as (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recess.

26. A program product, characterized in that The computer enables the substrate processing device to execute: (a) performing a cycle comprising the steps of simultaneously supplying a raw material gas to a substrate having a recessed portion formed on its surface, supplying a first nitrogen and hydrogen-containing gas to the substrate, supplying a second nitrogen and hydrogen-containing gas to the substrate, and supplying the first nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers of an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recessed portion, thereby forming an oligomer-containing layer on the surface of the substrate and in the recessed portion; as well as (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recess.

27. A program product, characterized in that The computer enables the substrate processing device to execute: (a) performing a cycle comprising the steps of supplying a raw material gas containing silicon and halogen to a substrate having a recess formed on its surface, supplying a first nitrogen and hydrogen gas to the substrate, and supplying a second nitrogen and hydrogen gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers of an element contained in at least one of the raw material gas, the first nitrogen and hydrogen gas, and the second nitrogen and hydrogen gas to generate, grow, and flow on the surface of the substrate and in the recess, thereby forming an oligomer-containing layer on the surface of the substrate and in the recess; as well as (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by the modified oligomer-containing layer in a manner that is buried in the recess.

28. A program product, characterized in that The computer enables the substrate processing device to execute: (a) performing a cycle comprising the steps of supplying a raw material gas to a substrate having a recessed portion formed on its surface, supplying a first nitrogen and hydrogen-containing gas to the substrate, and supplying a second nitrogen and hydrogen-containing gas to the substrate a predetermined number of times at a first temperature, thereby causing oligomers of an element contained in at least one of the raw material gas, the first nitrogen and hydrogen-containing gas, and the second nitrogen and hydrogen-containing gas to generate, grow, and flow on the surface of the substrate and in the recessed portion, thereby forming an oligomer-containing layer on the surface of the substrate and in the recessed portion; as well as (b) post-treating the substrate having the oligomer-containing layer formed on the surface of the substrate and in the recess at a second temperature higher than the first temperature, thereby modifying the oligomer-containing layer formed on the surface of the substrate and in the recess, and forming a film formed by embedding the modified oligomer-containing layer in the recess; (b) include: supplying at least one of a nitrogen-containing gas, a hydrogen-containing gas, and a nitrogen-and-hydrogen-containing gas to the substrate; and a step of supplying an oxygen-containing gas to the substrate.

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