Substrate processing method, semiconductor device manufacturing method, recording medium, substrate processing apparatus, and gas supply system

Abstract

The invention relates to a substrate processing method, a semiconductor device manufacturing method, a recording medium, a substrate processing apparatus, and a gas supply system. The present invention addresses the problem of providing a technique capable of improving the step coverage of a film formed on a substrate. A method for forming a film on a substrate includes forming a film on the substrate by performing a cycle for a predetermined number of times, the cycle including (a), (b), (c), and (d): (a) supplying a blocking agent to the substrate; (b) a step of supplying a first raw material from a first storage unit to the substrate; (c) a step of supplying a second raw material from a second storage unit to the substrate; and (d) a step for supplying a reaction body to the substrate.

Description

Technical Field

[0001] The present invention relates to a substrate processing method, a method for manufacturing a semiconductor device, a recording medium, a substrate processing apparatus, and a gas supply system. Background Art

[0002] As one of the substrate processing steps (semiconductor device manufacturing steps), a process of forming a film on a substrate is sometimes performed (for example, see Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2014-135475 Summary of the Invention

[0006] Problems to be solved by the invention

[0007] The present invention provides a technology capable of improving the step coverage (step coverage) of a film formed on a substrate.

[0008] Means for solving problems

[0009] According to one embodiment of the present invention, there is provided a technique comprising the step of forming a film on a substrate by performing a cycle including (a), (b), (c), and (d) a predetermined number of times, wherein:

[0010] (a) is a step of supplying an inhibitor to a substrate;

[0011] (b) a step of supplying a first raw material from a first storage portion to the substrate;

[0012] (c) a step of supplying a second raw material from a second storage portion to the substrate;

[0013] (d) is a step of supplying a reactant to the substrate.

[0014] Effects of the Invention

[0015] According to the present invention, the step coverage of a film formed on a substrate can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 1 is a schematic diagram of the structure of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present invention, and shows a portion of the processing furnace 202 in a vertical cross-sectional view.

[0017] Figure 2 This is a schematic diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present invention. Figure 1The AA line cross-sectional view shows a portion of the processing furnace 202 .

[0018] Figure 3 1 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a diagram showing a control system of the controller 121 in the form of a block diagram.

[0019] Figure 4 This is a diagram showing a processing procedure in one embodiment of the present invention.

[0020] Description of Reference Numerals

[0021] 200 wafers (substrates)

[0022] 240a 1st storage unit

[0023] 240b Second storage unit DETAILED DESCRIPTION

[0024] <One embodiment of the present invention>

[0025] The following mainly refers to Figures 1 to 4 One embodiment of the present invention will be described. It should be noted that the drawings used in the following description are schematic, and the dimensional relationships and ratios of the elements shown in the drawings may not necessarily be consistent with reality. Furthermore, the dimensional relationships and ratios of the elements shown in the multiple drawings may not necessarily be consistent with each other.

[0026] (1) Configuration of substrate processing apparatus

[0027] like Figure 1 As shown, the processing furnace 202 has a heater 207 as a temperature controller (heating 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 activates (excites) the gas by heat.

[0028] Inside heater 207, a reaction tube 203 is concentrically arranged with the heater 207. Reaction tube 203 is made of a heat-resistant material such as quartz or silicon carbide (SiC) and has a cylindrical shape with a closed upper end and an open lower end. Below reaction tube 203, a manifold 209 (hereinafter, MF209) is concentrically arranged with the reaction tube 203. The upper end of MF209 engages with the lower end of reaction tube 203 to support reaction tube 203. An O-ring 220a is provided as a sealing member between MF209 and reaction tube 203. Like heater 207, reaction tube 203 is mounted vertically. The reaction tube 203 and MF209 primarily constitute a processing vessel (reaction container). A processing chamber 201 is formed within the hollow portion of the processing container. Processing chamber 201 is configured to accommodate wafers 200, serving as substrates. Processing of wafers 200 is performed within this processing chamber 201.

[0029] Nozzles 249a to 249c, serving as the first to third supply units, are installed within processing chamber 201, penetrating the sidewalls of MF 209. These nozzles are also referred to as the first to third nozzles. These nozzles are made of a heat-resistant material, such as quartz or SiC. Gas supply pipes 232a to 232c are connected to these nozzles, respectively. These nozzles are different.

[0030] Gas supply pipes 232a and 232b are provided, in order from the upstream side of the gas flow, with mass flow controllers (MFCs) 241a and 241b, respectively, serving as flow controllers (flow control units); valves 243a and 243b, respectively, serving as on / off valves; a first reservoir 240a and a second reservoir 240b, each configured to temporarily store gas; and valves 242a and 242b. Gas supply pipes 232d and 232f are connected to gas supply pipe 232a downstream of valve 242a. Gas supply pipes 232e and 232g are connected to gas supply pipe 232b downstream of valve 242b. MFCs 241d to 241g and valves 243d to 243g are provided on gas supply pipes 232d to 232g, in order from the upstream side of the gas flow.

[0031] The first storage section 240a and the second storage section 240b are each configured as, for example, a gas tank or spiral piping having a larger gas capacity than conventional piping. By opening and closing valves 243a and 243b located upstream of the first storage section 240a and the second storage section 240b and valves 242a and 242b located downstream of the first storage section 240a and the second storage section 240b, respectively, the gas supplied from the gas supply pipes 232a and 232b can be filled into the first storage section 240a and the second storage section 240b, and the gas filled into the first storage section 240a and the second storage section 240b can be supplied into the processing chamber 201. The conductance between the first storage section 240a and the processing chamber 201 is preferably configured to be, for example, 1.5×10 -3 m 3 / s or more. Furthermore, considering the ratio of the volume of the processing chamber 201 to the volume of the first storage portion 240a, when the volume of the processing chamber 201 is 100 L (liters), the volume of the first storage portion 240a is preferably set to, for example, 100 to 300 cc, preferably, to a size of, for example, 1 / 1000 to 3 / 1000 times the volume of the processing chamber 201. The same applies to the second storage portion 240b.

[0032] By closing valves 242a and 242b and opening valves 243a and 243b, the gas whose flow rate has been regulated by MFCs 241a and 241b can be filled into the first and second reservoirs 240a and 240b, respectively. When the first and second reservoirs 240a and 240b are filled with a predetermined amount of gas and the pressures within the first and second reservoirs 240a and 240b reach predetermined pressures, valves 243a and 243b are closed and valves 242a and 242b are opened. This allows the high-pressure gas filled in the first and second reservoirs 240a and 240b to be supplied all at once (flash supply) into the processing chamber 201 in a short period of time via gas supply pipes 232a and 232b and nozzles 249a and 249b. It should be noted that valves 243a and 243b may also be open during flash supply.

[0033] Gas supply pipe 232c is provided with an MFC 241c and a valve 243c, serving as an on-off valve, in order from the upstream side of the gas flow. Gas supply pipe 232h is connected to gas supply pipe 232c downstream of valve 243c. Gas supply pipe 232h is provided with an MFC 241h and a valve 243h in order from the upstream side of the gas flow.

[0034] like Figure 2As shown, the nozzles 249a to 249c are provided in a circular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, extending from the lower portion of the inner wall of the reaction tube 203 along the upper portion toward the upper portion in the arrangement direction of the wafers 200. In other words, the nozzles 249a to 249c are provided along the wafer arrangement region, in regions that horizontally surround the wafer arrangement region and are located to the sides of the wafer arrangement region where the wafers 200 are arranged.

[0035] Nozzle 249a is positioned farther from the exhaust port 231a (described later) than nozzles 249b and 249c. Specifically, nozzles 249b and 249c are positioned closer to the exhaust port 231a than nozzle 249a. Furthermore, nozzles 249b and 249c are arranged symmetrically with respect to a line passing through the center of the wafer 200 (i.e., the center of the reaction tube 203) and the center of the exhaust port 231a when viewed from above. Furthermore, nozzles 249a and 249b are positioned so as to face each other on a straight line with the center of the reaction tube 203 sandwiched between them. In other words, nozzle 249b is positioned so as to face nozzle 249a.

[0036] Gas supply holes 250a to 250c are provided on the side surfaces of the nozzles 249a to 249c, respectively, for supplying gas. The gas supply holes 250a to 250c are each opened toward the center of the reaction tube 203, enabling gas to be supplied toward the wafer 200. The gas supply holes 250a and 250b are opened so as to face each other in a straight line, sandwiching the center of the wafer 200, i.e., the center of the reaction tube 203. A plurality of gas supply holes 250a to 250c are provided from the bottom to the top of the reaction tube 203.

[0037] The first raw material is supplied from the gas supply pipe 232 a into the processing chamber 201 via the MFC 241 a , the valve 243 a , the first storage portion 240 a , the valve 242 a , and the nozzle 249 a .

[0038] The second raw material is supplied from the gas supply pipe 232 b through the MFC 241 b , the valve 243 b , the second storage portion 240 b , the valve 242 b , and the nozzle 249 b into the processing chamber 201 .

[0039] The reactant 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 .

[0040] The first inhibitor (inhibitor) is supplied from the gas supply pipe 232 d into the processing chamber 201 via the MFC 241 d , the valve 243 d , and the nozzle 249 a .

[0041] The second inhibitor (inhibitor) is supplied from the gas supply pipe 232 e through the MFC 241 e , the valve 243 e , and the nozzle 249 b into the processing chamber 201 .

[0042] Inert gas is supplied from gas supply pipes 232f to 232h through MFCs 241f to 241h, valves 243f to 243h, 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, or dilution gas.

[0043] The first raw material supply system is primarily comprised of the gas supply pipe 232a, MFC 241a, valves 243a and 242a, and the first reservoir 240a. The second raw material supply system is primarily comprised of the gas supply pipe 232b, MFC 241b, valves 243b and 242b, and the second reservoir 240b. The reactant supply system is primarily comprised of the gas supply pipe 232c, MFC 241c, and valve 243c. The first supply system (first inhibitor supply system / inhibitor supply system) is primarily comprised of the gas supply pipe 232d, MFC 241d, and valve 243d. The second supply system (second inhibitor supply system) is primarily comprised of the gas supply pipe 232e, MFC 241e, and valve 243e. The inert gas supply system is primarily comprised of the gas supply pipes 232f to 232h, MFCs 241f to 241h, and valves 243f to 243h. It should be noted that the nozzles connected to the gas supply pipes constituting the various supply systems described above may be included in each of the supply systems. For example, the gas supply system may be composed of the first raw material supply system, the second raw material supply system, the reactant supply system, the first supply system, the second supply system, the inert gas supply system, and the controller 121 (described later) as the control unit.

[0044] Any or all of the various gas supply systems described above may be configured as an integrated gas supply system 248 that integrates valves 243a to 243h, 242a, and 242b, the first reservoir 240a, the second reservoir 240b, and MFCs 241a to 241h. The integrated gas supply system 248 is connected to the gas supply pipes 232a to 232h, respectively. The supply of various gases into the gas supply pipes 232a to 232h, i.e., the opening and closing of valves 243a to 243h, 242a, and 242b, and the flow rate adjustment by MFCs 241a to 241g, are controlled by a controller 121, described later. The integrated gas supply system 248 is constructed as an integrated unit of one piece or a split type, and can be installed and removed relative to the gas supply pipes 232a~232h, etc. as an integrated unit. The integrated gas supply system 248 can be maintained, replaced, and added as an integrated unit.

[0045] An exhaust port 231a is provided below the side wall of the reaction tube 203 to exhaust the atmosphere in the processing chamber 201. Figure 2 As shown, the exhaust port 231a is provided at a position opposite (facing) the nozzles 249a to 249c (gas supply holes 250a to 250c) sandwiching the wafer 200 when viewed from above. The exhaust port 231a may also be provided along the lower portion to the upper portion of the side wall of the reaction tube 203, i.e., along the wafer arrangement area. An exhaust pipe 231 serving as an exhaust path is connected to the exhaust port 231a. 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 in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 serving as a pressure regulator (pressure regulation unit). The APC valve 244, serving as an exhaust valve, is configured to open and close while the vacuum pump 246 is in operation, thereby enabling vacuum exhaust within the processing chamber 201 and stopping vacuum exhaust. Furthermore, while the vacuum pump 246 is in operation, the valve opening is adjusted based on pressure information detected by the pressure sensor 245, 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. It is also conceivable that the vacuum pump 246 may also be included in the exhaust system.

[0046] A sealing cover 219 (hereinafter referred to as SC219) is provided below MF209 as a furnace port cover that can airtightly seal the lower end opening of MF209. SC219 is made of a metal material such as SUS, for example, and is formed into a disc shape. On the upper surface of SC219, an O-ring 220b is provided as a sealing member that abuts against the lower end of MF209. A rotating mechanism 267 for rotating the wafer boat 217 described later is provided below SC219. The rotating shaft 255 of the rotating mechanism 267 is made of a metal material such as SUS, for example, and passes through SC219 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. SC219 is configured to be raised and lowered in the vertical direction by a wafer boat elevator 115 (hereinafter referred to as BE115) as a lifting mechanism provided outside the reaction tube 203. BE115 is configured as a transfer device (transfer mechanism) that moves the wafer 200 into and out of (transports) the processing chamber 201 by raising and lowering the SC 219 .

[0047] A gate 219s, serving as a furnace cover, is installed below the MF 209. This gate can airtightly seal the lower opening of the MF 209 when the SC 219 is lowered and the wafer boat 217 is unloaded from the processing chamber 201. The gate 219s is made 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 and abuts against the lower end of the MF 209. The opening and closing movements (such as lifting and rotating movements) of the gate 219s are controlled by a gate opening and closing mechanism 115s.

[0048] The wafer boat 217, serving as a substrate support, is configured to support multiple wafers 200, for example, 25 to 200, arranged in a horizontal position and aligned with each other's centers, arranged in multiple layers in a vertical direction. The wafer boat 217 is made of a heat-resistant material, such as quartz or SiC. Heat shields 218, also made of a heat-resistant material, such as quartz or SiC, are supported in multiple layers at the bottom of the wafer boat 217.

[0049] A temperature sensor 263 is provided within the reaction tube 203 as a temperature detector. By adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature within the processing chamber 201 is adjusted to a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0050] like Figure 3 As shown, the controller 121 as a control unit (control unit) is configured as a computer having a CPU (Central Processing Unit; Central Processing Unit) 121a, a RAM (Random Access Memory; 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 and output device 122, such as a touch panel, is connected to the controller 121. In addition, an external storage device 123 can be connected to the controller 121. It should be noted that the substrate processing apparatus can be configured to have one control unit or to have multiple control units. That is, one control unit or multiple control units can be used to control the processing sequence described later. In addition, the multiple control units can be configured as a control system interconnected by a wired or wireless communication network, or the control system as a whole can be used to control the processing sequence described later. When the term "control unit" is used in this specification, it includes not only one control unit but also a plurality of control units and a control system composed of a plurality of control units.

[0051] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. The control program for controlling the action of the substrate processing device, the process process that records the steps and conditions of the substrate processing described later, etc. are recorded and stored in a readable manner in the storage device 121c. The process process is composed of a method in which the substrate processing device executes the various steps in the substrate processing described later through the controller 121 and can obtain a specified result, and functions as a program. Hereinafter, the process process, control program, etc. are collectively referred to as a program. In addition, the process process is also referred to as a process. When the term "program" is used in this specification, sometimes only the process is included alone, sometimes only the control program is included alone, or sometimes both are included. RAM121b is configured as a memory area (work area) that temporarily holds the program, data, etc. read by CPU121a.

[0052] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241h, valves 243a to 243h, 242a, 242b, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, BE 115, gate opening and closing mechanism 115s, etc.

[0053] 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 input of an operation command from the input / output device 122. The CPU 121a is configured to perform the following operations according to the contents of the read recipe: flow rate control of various substances (gases) by the MFCs 241a to 241h; opening and closing of valves 243a to 243h, 242a, and 242b; opening and closing of the APC valve 244 and pressure control by the pressure sensor 245 and the APC valve 244; starting and stopping of the vacuum pump 246; temperature control of the heater 207 by the temperature sensor 263; rotation and rotation speed control of the wafer boat 217 by the rotation mechanism 267; raising and lowering of the wafer boat 217 by the BE 115; and opening and closing of the gate 219s by the gate opening and closing mechanism 115s.

[0054] The controller 121 can be constructed by installing the above-mentioned program recorded and stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a USB memory, a semiconductor memory such as an SSD, etc. The storage device 121c and the external storage device 123 constitute a recording medium that can be read by a computer. Hereinafter, they will be collectively referred to as recording media. When the term recording medium is used in this specification, sometimes only the storage device 121c is included alone, sometimes only the external storage device 123 is included alone, or sometimes both are included. It should be noted that, instead of using the external storage device 123, a communication unit such as the Internet or a dedicated line can be used to provide the program (program product) to the computer.

[0055] (2) Substrate processing

[0056] Main Use Figure 4 A method for processing a substrate using the above-described substrate processing apparatus as part of a semiconductor device manufacturing process will be described. Specifically, an example processing sequence for forming a film on a wafer 200, which is a substrate having recessed portions such as trenches, grooves, and holes formed on its surface as three-dimensional structures, will be described. In the following description, the operations of the various components of the substrate processing apparatus are controlled by a controller 121.

[0057] The processing sequence in this embodiment includes a step of performing a cycle including (a), (b), (c), and (d) a predetermined number of times (n times, where n is an integer of 1 or 2 or greater) to form a film on the wafer 200, wherein:

[0058] (a) is step A of supplying an inhibitor to the wafer 200;

[0059] (b) is step B of supplying the first raw material from the first storage portion 240a to the wafer 200;

[0060] (c) is step C of supplying the second raw material from the second storage portion 240b to the wafer 200;

[0061] (d) is step D of supplying the reactant to the wafer 200 .

[0062] It should be noted that step A may include at least one of step a1 of supplying a first inhibitor to the wafer 200 before step B and step a2 of supplying a second inhibitor to the wafer 200 before step C. As an example, Figure 4 This indicates a case where a cycle of step a1, step B, step a2, step C, and step D is performed a predetermined number of times (n times).

[0063] Right now, Figure 4The processing sequence shown shows an example of a step of forming a film on the wafer 200 by performing a cycle including the following steps a predetermined number of times (n times, where n is an integer of 1 or 2 or greater):

[0064] Step a1 of supplying a first inhibitor to the wafer 200;

[0065] Step B of supplying the first raw material from the first storage portion 240a to the wafer 200;

[0066] Step a2 of supplying a second inhibitor to the wafer 200;

[0067] Step C of supplying the second raw material from the second storage portion 240b to the wafer 200; and

[0068] Step D of supplying a reactant to the wafer 200 .

[0069] In this specification, for convenience, the above-mentioned processing sequence may be expressed as follows. The same expression is also used in the following description of modified examples and other aspects.

[0070] (first inhibitor → purge → first raw material → purge → second inhibitor → purge → second raw material → purge → reactant → purge) × n

[0071] In this specification, the term "wafer" may refer to the wafer itself or to a laminate of a wafer and a predetermined layer or film formed on its surface. The term "surface of a wafer" may refer to the surface of the wafer itself or to the surface of a predetermined layer, etc., formed on the wafer. In this specification, "forming a predetermined layer on a wafer" may refer to forming the predetermined layer directly on the surface of the wafer itself or to forming the predetermined layer on a layer, etc., formed on the wafer. The term "substrate" used in this specification is also synonymous with the term "wafer."

[0072] The term "agent" as used in this specification includes at least one of a gaseous substance and a liquid substance. A liquid substance includes a mist substance. That is, the inhibitor (the first inhibitor and the second inhibitor) may each include a gaseous substance, a liquid substance such as a mist substance, or both.

[0073] The term "layer" used in this specification includes at least one of a continuous layer and a discontinuous layer. For example, the first to third layers described below may include a continuous layer, a discontinuous layer, or both.

[0074] In this specification, when describing the adsorption and reaction of the first inhibitor, the second inhibitor, the first raw material, the second raw material and the reactant on the surface of the chip 200, it not only includes the way in which they adsorb and react on the surface of the chip in an undecomposed state, but also includes the way in which the intermediates generated by their decomposition or the detachment of their ligands adsorb and react on the surface of the chip 200.

[0075] (Wafer filling and wafer boat loading)

[0076] After a plurality of wafers 200 are loaded (wafer filling) into the wafer boat 217, the gate 219s is moved by the gate opening and closing mechanism 115s to open the lower end opening of the MF 209 (gate opening). Figure 1 As shown, the boat 217 supporting a plurality of wafers 200 is lifted by the BE 115 and carried (boat loading) into the processing chamber 201. In this state, the SC 219 seals the lower end of the MF 209 via the O-ring 220b.

[0077] (Pressure regulation and temperature regulation)

[0078] After the wafer boat is loaded, vacuum exhaust (decompression exhaust) is performed by the vacuum pump 246 to make the space in the processing chamber 201 where the wafer 200 is located reach the desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback controlled (pressure regulated) based on the measured pressure information. In addition, heating is performed by the heater 207 to make the wafer 200 in the processing chamber 201 reach the desired processing temperature. At this time, the power supplied to the heater 207 is feedback controlled based on the temperature information detected by the temperature sensor 263 to achieve the desired temperature distribution (temperature regulation) in the processing chamber 201. In addition, the rotation of the wafer 200 by the rotation mechanism 267 is started. The exhaust in the processing chamber 201, the heating and rotation of the wafer 200 are all continued for at least until the processing of the wafer 200 is completed.

[0079] (Film forming treatment)

[0080] Afterwards, the following steps a1, B, a2, C, and D are performed in sequence.

[0081] [Step a1]

[0082] In this step, a first inhibitor is supplied to the wafer 200 in the processing chamber 201 .

[0083] Specifically, valve 243d is opened to allow the first inhibitor to flow into gas supply pipe 232d. The first inhibitor, with its flow rate regulated by MFC 241d, is supplied into processing chamber 201 via nozzle 249a and exhausted from exhaust port 231a. At this point, the first inhibitor is supplied to wafer 200 (first inhibitor supply). Alternatively, valves 243f through 243h may be opened to supply inert gas into processing chamber 201 via nozzles 249a through 249c, respectively.

[0084] As treatment conditions when supplying the first inhibitor in step a1, the following can be exemplified:

[0085] Processing temperature: 250-800°C, preferably 600-700°C

[0086] Processing pressure: 1~3990Pa, preferably 10~1333Pa

[0087] First inhibitor supply flow rate: 0.005-5 slm, preferably 0.1-1 slm

[0088] First inhibitor supply time: 10 to 120 seconds, preferably 20 to 60 seconds

[0089] Inert gas supply flow rate (per gas supply pipe): 0 to 10 slm

[0090] It should be noted that the expression of a numerical range such as "250 to 800°C" in this specification means that the lower limit and the upper limit are included in the range. Therefore, for example, "250 to 800°C" means "above 250°C and below 800°C". The same applies to other numerical ranges. In addition, the processing temperature in this specification refers to the temperature of the wafer 200 or the temperature in the processing chamber 201, and the processing pressure refers to the pressure in the processing chamber 201. In addition, the processing time refers to the time during which the processing continues. In addition, the supply flow rate refers to the flow rate of the gas supplied to the processing chamber 201. In addition, when the supply flow rate includes 0slm, 0slm means that the substance (gas) is not supplied. This is also the case in the following description.

[0091] By supplying the first inhibitor to the wafer 200 under the aforementioned processing conditions, the first inhibitor can be adsorbed to adsorption sites on the surface of the wafer 200. Specifically, the first inhibitor can be adsorbed to at least a portion of the upper and inner surfaces (specifically, the inner side and bottom surfaces of the recesses) of the recesses formed on the surface of the wafer 200. More specifically, the first inhibitor can be preferentially adsorbed to the open side (upper side) of the recesses as compared to the deeper side.

[0092] As the first inhibitor, a gas containing at least any one of chlorine (Cl), fluorine (F), bromine (Br), and iodine (I) as a halogen can be used. As the first inhibitor, for example, a single substance gas of a halogen such as Cl2 gas, F2 gas, Br2 gas, or I2 gas, a halogen compound gas such as ClF3 gas, BrCl gas, ICl gas, IF5 gas, BrF3 gas, or IBr gas, a hydrogen halide compound gas such as HCl gas, HF gas, HBr gas, or HI gas, or a gas formed by combining these gases can be used. In addition, a halogen-containing free radical (Cl2) generated by activating these gases by plasma excitation or the like can be used. * 、F * Br * , I * As the first inhibitor, one or more of these may be used.

[0093] In addition, a gas containing an organic compound can be used as the first inhibitor. As the gas containing an organic compound, a gas containing at least one selected from the group consisting of ether compounds, ketone compounds, amine compounds, organic hydrazine compounds, and compounds having a cyclic structure in their molecular structure can be used. As the gas containing an ether compound, a gas containing at least one of dimethyl ether, diethyl ether, methyl ethyl ether, propyl ether, isopropyl ether, furan, tetrahydrofuran, pyran, tetrahydropyran, etc. can be used. As the gas containing a ketone compound, a gas containing at least one of dimethyl ketone, diethyl ketone, methyl ethyl ketone, methyl propyl ketone, etc. can be used. As the gas containing an amine compound, a gas containing at least one of methylamine compounds such as monomethylamine, dimethylamine, and trimethylamine; ethylamine compounds such as monoethylamine, diethylamine, and triethylamine; and methylethylamine compounds such as dimethylethylamine and methyldiethylamine can be used. As the gas containing an organic hydrazine compound, a gas containing at least one of methylhydrazine-based gases such as monomethylhydrazine, dimethylhydrazine, and trimethylhydrazine can be used. As the gas containing a compound having a cyclic structure, gases such as methoxycyclopentane, anisole, and 1,3-propylene oxide, which have a cyclic structure containing at least one of a cycloalkyl group, a benzene ring structure, and carbon in their molecular structure, can be used. As the first inhibitor, one or more of these can be used.

[0094] Alternatively, an alkyl group-containing gas containing an alkyl group may be used as the first inhibitor. Examples of the first inhibitor include CH 4 gas, C 2 H 6 gas, and C 3 H 8 gas.

[0095] As the inert gas, rare gases such as N2 gas, Ar gas, He gas, Ne gas, and Xe gas can be used. As the inert gas, one or more of these can be used. This also applies to the steps described below.

[0096] After the first inhibitor is adsorbed on the surface of the wafer 200, valve 243d is closed to stop the supply of the first inhibitor into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove gaseous substances and the like remaining therein. At this point, valves 243f to 243h are opened to supply an inert gas into the processing chamber 201 via nozzles 249a to 249c. The inert gas supplied from nozzles 249a to 249c acts as a purge gas, thereby purging (purging) the space within the processing chamber 201 where the wafer 200 is located.

[0097] It should be noted that during step a1, valve 242a is closed and valve 243a is opened to allow the first raw material to flow into gas supply pipe 232a. The first raw material is flow-regulated by MFC 241a and supplied to first reservoir 240a. Thus, first reservoir 240a is filled with the first raw material (first tank filling). After a predetermined amount of the first raw material is charged into first reservoir 240a, valve 243a is closed to maintain the first raw material in the first reservoir 240a. First tank filling can also be performed before step a1 is executed.

[0098] [Step B]

[0099] In this step, a first raw material is supplied to the wafer 200 in the processing chamber 201 .

[0100] Specifically, valve 242a is opened to allow the high-pressure first raw material filled in the first storage portion 240a to flow into the processing chamber 201 at once. Thus, the first raw material is supplied to the chip 200 at once (flash supply of the first raw material). In the flash supply of the first raw material, due to the pressure difference between the first storage portion 240a and the processing chamber 201, the first raw material ejected from the nozzle 249a into the processing chamber 201 is accelerated to, for example, the speed of sound (340 m / sec), and the speed of the first raw material on the chip 200 also reaches about tens of m / sec. The same is true for the flash supply of the second raw material described later. At this time, valve 243a is opened in advance. At this time, valves 243f to 243h can also be opened to supply inert gas into the processing chamber 201 through nozzles 249a to 249c, respectively.

[0101] As the treatment conditions when the first raw material is supplied in step B, the following can be exemplified:

[0102] Processing temperature: 250-800°C, preferably 600-700°C

[0103] Processing pressure: 1~2666Pa, preferably 1~1333Pa

[0104] First raw material supply flow rate: 0.001 to 5 slm, preferably 0.1 to 5 slm

[0105] First raw material supply time: 0.1 to 20 seconds, preferably 0.5 to 5 seconds

[0106] Inert gas supply flow rate (per gas supply pipe): 0 to 10 slm

[0107] By supplying the first raw material to the wafer 200 under the above-described processing conditions, the first raw material can be adsorbed to portions of the surface of the wafer 200 where the first inhibitor is not adsorbed, that is, adsorption sites remaining on the surface of the wafer 200 , thereby forming the first layer.

[0108] Here, the first inhibitor is a substance that inhibits the adsorption of the first raw material onto wafer 200. Specifically, the functional groups (e.g., halogen groups) contained in the first inhibitor, formed (exposed) on the upper and inner surfaces of the recesses, inhibit the adsorption of the first raw material onto wafer 200 (on the upper and inner surfaces of the recesses). As described above, the first inhibitor preferentially adsorbs on the open side of the recess, thus suppressing the adsorption of the first raw material more on the open side than on the deep side of the recess. This allows the first raw material to preferentially adsorb on the deep side of the recess, thereby forming the first layer.

[0109] Furthermore, in this method, by flash-feeding the first raw material, a large flow rate of the first raw material can be supplied to the wafer 200 in a short period of time from the start of supply of the first raw material. This increases the amount of the first raw material that reaches the deep side of the recess in a short period of time from the start of supply of the first raw material. Consequently, the first raw material can be preferentially adsorbed to the deep side of the recess, thereby forming the first layer.

[0110] As the first raw material, for example, a silane-based gas containing silicon (Si), which is the main element constituting the film formed on the wafer 200, can be used. As the silane-based gas, for example, a gas containing Si and a halogen, i.e., a halosilane-based gas, can be used. Halogens include Cl, F, Br, I, etc. As the halosilane-based gas, for example, a chlorosilane-based gas containing Si and Cl can be used.

[0111] As the first raw material, for example, chlorosilane-based gases such as SiH3Cl gas, SiH2Cl2 gas, SiHCl3 gas, SiCl4 gas, Si2Cl6 gas, Si3Cl8 gas, Si2Cl6 gas, Si3Cl8 gas, Si2H5Cl gas, Si2H4Cl2 gas, Si2H3Cl3 gas, Si2H2Cl4 gas, Si3H5Cl gas, and Si3H4Cl2 gas can be used. One or more of these gases can be used as the first raw material.

[0112] As the first raw material, in addition to chlorosilane-based gases, fluorosilane-based gases such as SiF4 gas and SiH2F2 gas, bromosilane-based gases such as SiBr4 gas and SiH2Br2 gas, and iodosilane-based gases such as SiI4 gas and SiH2I2 gas can be used. One or more of these gases can be used as the first raw material.

[0113] As the first raw material, in addition to the above raw materials, for example, a gas containing Si and an amino group, i.e., an aminosilane-based gas, can also be used. Amino refers to a monovalent functional group formed by removing hydrogen (H) from ammonia, a primary amine, or a secondary amine, and can be represented by -NH2, -NHR, or -NR2. It should be noted that R represents an alkyl group, and the two Rs in -NR2 can be the same or different.

[0114] As the first raw material, for example, aminosilane-based gases (organoaminosilane-based gases) such as (Si[N(CH3)2]4) gas, (Si[N(CH3)2]3H) gas, (Si[N(C2H5)2]2H2) gas, (SiH2[NH(C4H9)]2) gas, and (SiH3[N(C3H7)2]) gas can be used. One or more of these can be used as the first raw material.

[0115] After the first layer is formed on the surface of the wafer 200, the valves 243a and 242b are closed to stop the supply of the first raw material into the processing chamber 201. Thereafter, the same process as the above (purge) is performed.

[0116] [Step a2]

[0117] In this step, the second inhibitor is supplied to the wafer 200 in the processing chamber 201 .

[0118] Specifically, valve 243e is opened to allow the second inhibitor to flow into gas supply pipe 232e. The second inhibitor, with its flow rate regulated by MFC 241e, is supplied into processing chamber 201 via nozzle 249b and exhausted from exhaust port 231a. At this point, the second inhibitor is supplied to wafer 200 (second inhibitor supply). Alternatively, valves 243f through 243h may be opened to supply inert gas into processing chamber 201 via nozzles 249a through 249c, respectively.

[0119] As the treatment conditions when supplying the second inhibitor in step a2, the following can be exemplified:

[0120] Processing temperature: 250-800°C, preferably 600-700°C

[0121] Processing pressure: 1~3990Pa, preferably 10~1333Pa

[0122] Second inhibitor supply flow rate: 0.005-5 slm, preferably 0.1-1 slm

[0123] Second inhibitor supply time: 10 to 120 seconds, preferably 20 to 60 seconds

[0124] Inert gas supply flow rate (per gas supply pipe): 0 to 10 slm

[0125] By supplying the second barrier agent to the wafer 200 under the aforementioned processing conditions, the second barrier agent can be adsorbed onto portions of the wafer 200 surface to which the first barrier agent is not adsorbed. Specifically, the second barrier agent can be adsorbed onto portions of at least a portion of the upper and inner surfaces (specifically, the inner side surfaces and bottom surfaces) of the recesses formed on the surface of the wafer 200, to which the first barrier agent is not adsorbed. More specifically, the second barrier agent can be preferentially adsorbed onto the open side of the recesses compared to the deep side.

[0126] As the second inhibitor, for example, one or more of the gases exemplified as the first inhibitor can be used. The second inhibitor may be the same gas as the first inhibitor or a different gas from the first inhibitor.

[0127] After the second inhibitor is adsorbed on the surface of the wafer 200, the valve 243e is closed to stop the supply of the first raw material into the processing chamber 201. Thereafter, the same process as the above (purge) is performed.

[0128] It should be noted that during the execution of step a2, valve 242b is closed and valve 243b is opened to allow the second raw material to flow into gas supply pipe 232b. The second raw material is flow-regulated by MFC 241b and supplied to the second storage section 240b. Thus, the second raw material is filled into the second storage section 240b (the second tank is filled). After the second storage section 240b has been filled with a predetermined amount of the second raw material, valve 243b is closed to maintain the second storage section 240b filled with the second raw material. The second tank filling can also be performed before the execution of step a2.

[0129] [Step C]

[0130] In this step, the second raw material is supplied to the wafer 200 in the processing chamber 201 .

[0131] Specifically, valve 242b is opened to allow the high-pressure second raw material filled in second reservoir 240b to flow into processing chamber 201 all at once. This allows the second raw material to be supplied all at once to wafers 200 (flash supply of the second raw material). At this time, valve 243b is previously opened. Alternatively, valves 243f through 243h may be opened to supply inert gas into processing chamber 201 through nozzles 249a through 249c, respectively.

[0132] As the treatment conditions when the second raw material is supplied in step C, the following can be exemplified:

[0133] Processing temperature: 250-800°C, preferably 600-700°C

[0134] Processing pressure: 1~2666Pa, preferably 1~1333Pa

[0135] Second raw material supply flow rate: 0.001 to 5 slm, preferably 0.1 to 5 slm

[0136] Second raw material supply time: 0.1 to 20 seconds, preferably 0.5 to 5 seconds

[0137] Inert gas supply flow rate (per gas supply pipe): 0 to 10 slm

[0138] By supplying the second raw material to the chip 200 under the above-mentioned processing conditions, the second raw material can be adsorbed on the surface of the chip 200 where at least one of the first inhibitor and the second inhibitor is not adsorbed (in other words, where neither the first inhibitor nor the second inhibitor is adsorbed), thereby forming a second layer.

[0139] Here, both the first and second inhibitors are substances that inhibit the adsorption of the second raw material onto the wafer 200. Specifically, the functional groups (e.g., halogen groups) contained in the first and second inhibitors, which are formed (exposed) on the upper and inner surfaces of the recesses, inhibit the adsorption of the second raw material onto the wafer 200 (on the upper and inner surfaces of the recesses). As described above, both the first and second inhibitors preferentially adsorb on the open side of the recesses, thus suppressing the adsorption of the second raw material more on the open side than on the deep side of the recesses. This allows the second raw material to preferentially adsorb on the deep side of the recesses, forming the second layer.

[0140] Furthermore, in this method, by flash-feeding the second raw material, a large flow rate of the second raw material can be supplied to the wafer 200 in a short period of time from the start of supply of the second raw material. This increases the amount of the second raw material that reaches the deep side of the recess in a short period of time from the start of supply of the second raw material. Consequently, the second raw material can be preferentially adsorbed to the deep side of the recess, forming the second layer.

[0141] As the second raw material, for example, one or more of the gases exemplified as the first raw material can be used. The second raw material may use the same raw material gas (same material) as the first raw material, but preferably uses a different raw material gas (different material) from the first raw material.

[0142] After the second layer is formed on the surface of the wafer 200, the valves 243b and 242b are closed to stop the supply of the second raw material into the processing chamber 201. Thereafter, the same process as the above (purge) is performed.

[0143] [Step D]

[0144] After step C is completed, the reactant is supplied to the wafer 200 in the processing chamber 201 .

[0145] Specifically, valve 243c is opened to allow the reactant to flow into gas supply pipe 232c. The reactant is flow-regulated by MFC 241c and supplied into processing chamber 201 via nozzle 249c and exhausted from exhaust port 231a. At this point, the reactant is supplied to wafer 200 (reactant supply). Alternatively, valves 243e through 243g may be opened to supply inert gas into processing chamber 201 via nozzles 249a through 249c, respectively.

[0146] As the treatment conditions when the reactants are supplied in step D, the following can be exemplified:

[0147] Processing temperature: 400-800°C, preferably 650-700°C

[0148] Processing pressure: 10-10000Pa, preferably 20-5000Pa

[0149] Reactant supply flow rate: 0.001 to 20 slm, preferably 1 to 10 slm

[0150] Reactant supply time: 1 to 120 seconds, preferably 1 to 60 seconds

[0151] Inert gas supply flow rate (per gas supply pipe): 0 to 10 slm

[0152] By supplying the reactant to wafer 200 under the aforementioned processing conditions, at least a portion of the first and second layers formed on wafer 200 reacts with the reactant and is modified. As a result, a third layer is formed on wafer 200, specifically on the inner surface of the recessed portion, as a modified layer of at least one of the first and second layers.

[0153] As a reactant, for example, a gas containing nitrogen (N) and hydrogen (H) as a nitriding gas can be used. The gas containing N and H is both a gas containing N and a gas containing H. The gas containing N and H preferably has an NH bond.

[0154] As the reactant, for example, a hydrogen nitride gas such as NH 3 gas, N 2 H 2 gas, N 2 H 4 gas, or N 3 H 8 gas can be used.

[0155] As a reactant, in addition to the reactants described above, a gas containing nitrogen, carbon (C), and hydrogen can be used. Examples of the gas containing nitrogen, carbon, and hydrogen include amine-based gases and organic hydrazine-based gases. The gas containing nitrogen, carbon, and hydrogen is a gas containing nitrogen, carbon, hydrogen, and nitrogen and carbon.

[0156] As reactants, for example, ethylamine gases such as C2H5NH2 gas, (C2H5)2NH gas, (C2H5)3N gas, methylamine gases such as CH3NH2 gas, (CH3)2NH gas, (CH3)3N gas, organic hydrazine gases such as (CH3)HN2H2 gas, (CH3)2N2H2 gas, (CH3)2N2(CH3)H gas, etc. can be used.

[0157] As the reactant, one or more of the above-mentioned reactants can be used.

[0158] After the third layer is formed on the surface of the wafer 200, the valve 243c is closed to stop the supply of the reactant into the processing chamber 201. Then, the same process as the above (purge) is performed.

[0159] [Number of times of implementation]

[0160] By performing the above-mentioned steps a1, B, a2, C, and D in a non-simultaneous, i.e., asynchronous, cycle n times (n is an integer greater than or equal to 1 or 2), a film can be formed on the surface (inner surface of the recess) of the wafer 200. In addition, by setting the number of cycles n as the number of times the interior of the recess is filled with the film, the interior of the recess is filled with the film. For example, when the above-mentioned Si-containing gas is used as the first raw material and the second raw material, and the above-mentioned nitriding gas is used as the reactant, a silicon nitride film (SiN film) is formed on the surface of the wafer 200. The above-mentioned cycle is preferably repeated multiple times. That is, it is preferred that the thickness of the third layer formed in each cycle is thinner than the desired film thickness, and the above-mentioned cycle is repeated multiple times until the film thickness of the film formed by stacking the third layer reaches the desired film thickness. In addition, in the cycle after the second cycle, it is preferred that the first raw material in step B is filled into the first storage portion 240a in parallel with the supply of the reactant in step D of the previous cycle.

[0161] (Post-purge and atmospheric pressure recovery)

[0162] After the film of the desired thickness is formed on the wafer 200, 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. Thus, the processing chamber 201 is purged, and the gas, reaction byproducts, etc. remaining in the processing chamber 201 are removed from the processing chamber 201. The atmosphere in the processing chamber 201 is then replaced with the inert gas, and the pressure in the processing chamber 201 is restored to normal pressure (return to atmospheric pressure).

[0163] (Wafer boat unloading and wafer removal)

[0164] Afterwards, the SC 219 is lowered by the BE 115, opening the lower end of the MF 209. The processed wafers 200, supported on the wafer boat 217, are then unloaded from the lower end of the MF 209 (boat unloading) to the exterior of the reaction tube 203. After the boat is unloaded, the gate 219s is moved, sealing the lower end of the MF 209 with the gate 219s via the O-ring 220c. After the processed wafers 200 are unloaded from the reaction tube 203, they are removed from the wafer boat 217.

[0165] (3) Effects of this method

[0166] According to this aspect, one or more of the following effects can be obtained.

[0167] The first and second inhibitors supplied in steps a1 and a3 are preferentially adsorbed on the opening side of the recess compared to the deep side. Therefore, the first and second raw materials supplied in steps B and C are more suppressed on the opening side than on the deep side of the recess. This allows the first and second raw materials to be preferentially adsorbed on the deep side of the recess, enabling film formation at a uniform rate from the deep side to the opening within the recess. This improves step coverage.

[0168] In steps B and C, the first raw material and the second raw material are respectively pre-filled into the first storage portion 240a and the second storage portion 240b, and then supplied into the processing chamber 201. That is, a large flow rate of the first raw material and the second raw material is supplied in one go (flash supply) in a short period of time. As a result, the amount of the first raw material and the second raw material that reaches the deep side of the recess in a short period of time from the start of the supply of the first raw material and the second raw material can be increased. Therefore, the first raw material and the second raw material can be more preferentially adsorbed on the deep side of the recess, so that the film can be formed at a more uniform rate from the deep side of the recess to the opening side. As a result, the step coverage can be further improved.

[0169] By using materials with different amounts of Si per molecule as the first and second raw materials, or by using different materials such as an organic material for one and an inorganic material for the other, the raw materials (first and second raw materials) can be uniformly adsorbed onto the wafer 200. This allows for more uniform adsorption of the first and second raw materials from the deep side of the recess to the open side. Consequently, the step coverage can be further improved.

[0170] Furthermore, by supplying both the first inhibitor that inhibits adsorption of the first raw material and the first raw material from nozzle 249a, adsorption of the first raw material to nozzle 249a can be prevented. Similarly, by supplying both the second inhibitor that inhibits adsorption of the second raw material and the second raw material from nozzle 249b, adsorption of the second raw material to nozzle 249b can be prevented.

[0171] (4) Modification

[0172] The processing sequence in this mode can be changed as in the following modification examples. These modification examples can be combined arbitrarily. As long as there is no special explanation, the processing steps and treatment conditions in each step of each modification example can be made the same as the processing steps and treatment conditions in each step of the above-mentioned processing sequence.

[0173] (Variation 1)

[0174] As in the processing sequence shown below, step a2 may not be performed, and steps a1, B, C, and D may be performed in sequence.

[0175] (first inhibitor → purge → first raw material → purge → second raw material → purge → reactant → purge) × n

[0176] In this modification, the same effects as those of the above embodiment can be obtained. In this modification, the cycle time can be further shortened and productivity can be improved.

[0177] (Variation 2)

[0178] As in the processing sequence shown below, step a1 may not be performed, and steps B, a2, C, and D may be performed in sequence.

[0179] (first raw material → purge → second inhibitor → purge → second raw material → purge → reactant → purge) × n

[0180] In this modification, the same effects as those of the above embodiment can be obtained. In this modification, the cycle time can be further shortened and productivity can be improved.

[0181] (Variation 3)

[0182] As shown in the following processing sequence, step a2 may not be performed, and steps a1, B, and D may be performed in sequence, and step C may be performed simultaneously with step B.

[0183] {first inhibitor → purge → (first raw material + second raw material) → purge → reactant → purge}×n

[0184] In this modification, the same effects as those of the above embodiment can be obtained. In this modification, the cycle time can be further shortened and productivity can be improved.

[0185] (Variation 4)

[0186] As shown in the following processing sequence, step a1 may not be performed, and steps B, a2, C, and D may be performed in sequence. Step C may also be performed when step B is performed, and step B may also be performed when step C is performed.

[0187] {(first raw material + second raw material) → purge → second inhibitor → purge → (first raw material + second raw material) → purge → reactant → purge}×n

[0188] This modification also provides the same effects as those of the above embodiment. In this modification, the amount of the first and second raw materials adsorbed onto the wafer 200 per cycle can be increased, thereby improving productivity.

[0189] (Variant 5)

[0190] As in the processing sequence shown below, step a1 may not be performed, and steps B, a2, C, and D may be performed in sequence, and step C may also be performed when step B is performed.

[0191] {(first raw material + second raw material) → purge → second inhibitor → purge → second raw material → purge → reactant → purge}×n

[0192] This variation also achieves the same effects as the above-described method. In this variation, a relatively large amount of the first raw material can be adsorbed on the deep side of the recess in step B, while a relatively large amount of the second raw material can be adsorbed on the open side of the recess in step C. This allows for film formation at a uniform rate from the deep side to the open side within the recess, improving film thickness uniformity within the recess and, in particular, increasing step coverage when forming the film in the recess. Furthermore, this variation reduces the amount of raw materials compared to variations such as variation 4, which simultaneously performs steps B and C twice.

[0193] (Variant 6)

[0194] As in the processing sequence shown below, step a1 may not be performed, and steps B, a2, C, and D may be performed in sequence, and step B may also be performed when step C is performed.

[0195] {first raw material → purge → second inhibitor → purge → (first raw material + second raw material) → purge → reactant → purge}×n

[0196] In this modification, also can obtain the same effect as above-mentioned mode. In this modification, can further shorten cycle time and improve productivity. In addition, compared with modification 4 etc. which will carry out step B and step C simultaneously and carry out 2 times, can reduce raw materials.

[0197] (Variant 7)

[0198] Alternatively, as shown in the following processing sequence, steps a1, B, a2, C, and D may be performed in sequence, and step C may be performed when step B is performed, and step B may be performed when step C is performed.

[0199] {first inhibitor → purge → (first raw material + second raw material) → purge → second inhibitor → purge → (first raw material + second raw material) → purge → reactant → purge}×n

[0200] This modification also provides the same effects as those of the above embodiment. This modification also increases the amount of the first and second raw materials adsorbed onto the wafer 200 per cycle, thereby improving productivity.

[0201] (Variation 8)

[0202] Alternatively, as shown in the following processing sequence, steps a1, B, a2, C, and D may be performed in sequence, and step C may also be performed when step B is performed.

[0203] {first inhibitor → purge → (first raw material + second raw material) → purge → second inhibitor → purge → second raw material → purge → reactant → purge}×n

[0204] This variation also achieves the same effects as the above-described method. In this variation, a relatively large amount of the first raw material can be adsorbed on the deep side of the recess in step B, while a relatively large amount of the second raw material can be adsorbed on the open side of the recess in step C. This allows for film formation at a uniform rate from the deep side to the open side within the recess, improving film thickness uniformity within the recess and, in particular, increasing step coverage when forming the film in the recess. Furthermore, this variation reduces the amount of raw materials compared to variations such as Example 7, which simultaneously performs steps B and C twice.

[0205] (Variant 9)

[0206] Alternatively, as shown in the following processing sequence, steps a1, B, a2, C, and D may be performed in sequence, and step B may also be performed when step C is performed.

[0207] {first inhibitor → purge → first raw material → purge → second inhibitor → purge → (first raw material + second raw material) → purge → reactant → purge}×n

[0208] This modification also achieves the same effects as the above-described embodiment. This modification also increases the amount of the first and second raw materials adsorbed onto wafer 200 per cycle, thereby improving productivity. Furthermore, compared to Modification 7, which performs Step B and Step C simultaneously twice, it also reduces the amount of raw materials.

[0209] <Other aspects of the present invention>

[0210] The embodiments of the present invention have been specifically described above. However, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit and scope of the present invention.

[0211] For example, by varying the amounts of the first and second raw materials (tank filling amounts) filled into the first reservoir 240a and second reservoir 240b, the adsorption of the first and second raw materials onto the wafer 200 in steps B and C can be adjusted. For example, if the amount of the first raw material filled into the first reservoir 240a is greater than the amount of the second raw material filled into the second reservoir 240b, a higher flow rate of the first raw material is supplied to the wafer 200 in a shorter period of time than the second raw material. Consequently, a greater amount of the first raw material supplied in step B is adsorbed onto the deep side of the recess compared to the second raw material supplied in step C. In other words, in step B, a relatively large amount of the first raw material can be adsorbed onto the deep side of the recess, while in step C, a relatively large amount of the second raw material can be adsorbed onto the open side of the recess. This method also achieves the same effects as the above-described method.

[0212] On the other hand, when the amount of the second raw material filled in the second reservoir 240b is greater than the amount of the first raw material filled in the first reservoir 240a, a larger flow rate of the second raw material is supplied to the wafer 200 in a shorter time than the first raw material. Therefore, a larger amount of the second raw material supplied in step C is adsorbed toward the deep side of the recess compared to the first raw material supplied in step B. In other words, in step B, a relatively large amount of the first raw material can be adsorbed toward the open side of the recess, while in step C, a relatively large amount of the second raw material can be adsorbed toward the deep side of the recess. This embodiment also achieves the same effects as the above-described embodiment.

[0213] For example, by varying the supply amounts of the first and second inhibitors, the adsorption states of the first and second raw materials onto the wafer 200 in steps B and C can be adjusted. For example, if the supply amount of the first inhibitor is greater than the supply amount of the second inhibitor, the first inhibitor supplied in step a1 is more adsorbed toward the opening side of the recess than the second inhibitor supplied in step a2. Consequently, the first raw material supplied in step B is less adsorbed toward the opening side of the recess than the second raw material supplied in step C, resulting in a greater adsorption toward the deeper side of the recess. In other words, in step B, a relatively large amount of the first raw material can be adsorbed toward the deeper side of the recess, while in step C, a relatively large amount of the second raw material can be adsorbed toward the opening side of the recess. This method also achieves the same effects as the above-described method.

[0214] On the other hand, when the supply amount of the second inhibitor is greater than the supply amount of the first inhibitor, the second inhibitor supplied in step a2 is more likely to be adsorbed toward the opening side of the recess than the first inhibitor supplied in step a1. Therefore, compared to the first raw material supplied in step B, the second raw material supplied in step C is less likely to be adsorbed toward the opening side of the recess and is therefore more likely to be adsorbed toward the deep side of the recess. In other words, in step C, a relatively large amount of the second raw material can be adsorbed toward the deep side of the recess, while in step B, a relatively large amount of the first raw material can be adsorbed toward the opening side of the recess. This method also achieves the same effects as the above-described method.

[0215] In the above-mentioned method, in steps B and C, the case where the first raw material and the second raw material are respectively supplied at a flash speed is described as an example. However, the present invention is not limited to this. For example, before executing step B, the first raw material may not be pre-filled into the first storage portion 240a, but the first raw material may be supplied (non-flash supply, normal flow) into the processing chamber 201 via valve 243a, the first storage portion 240a, valve 242a, nozzle 249a, etc. Alternatively, before executing step C, the second raw material may not be pre-filled into the second storage portion 240b, but the second raw material may be supplied (non-flash supply, normal flow) into the processing chamber 201 via valve 243b, the second storage portion 240b, valve 242a, nozzle 249b, etc. In this method, at least a part of the effects described in the above-mentioned method can also be obtained.

[0216] In the above-mentioned method, the case where the first inhibitor and the second inhibitor hinder the first raw material and the second raw material from being adsorbed on the surface of the chip 200 is described as an example. However, the present invention is not limited to this. For example, the first inhibitor and the second inhibitor can also be used as a modifier, a treatment agent, a promoter or a dopant. As an example, the first inhibitor can be used as an inhibitor in step a1, and the second inhibitor can be used as a treatment agent or a dopant in step a2. Here, in the case where the second inhibitor is used as a treatment agent, as the second inhibitor, for example, a gas containing O and H, a gas containing O, a gas containing O and N, a gas containing O and C, etc. can be used. When the second inhibitor is used as a dopant, as the second inhibitor, for example, trichloroborane (BCl3) gas, phosphine (PH3) gas, etc. can be used. In this method, at least a part of the effects described in the above-mentioned method can also be obtained.

[0217] In addition, in the above-mentioned method, as the first raw material, chlorosilane gas is used as an example. However, the present invention is not limited to this. For example, using a first raw material containing a metal element such as aluminum (Al), titanium (Ti), hafnium (Hf), zirconium (Zr), tantalum (Ta), molybdenum (Mo), tungsten (W), and forming an AlN film, TiN film, HfN film, ZrN film, TaN film, molybdenum nitride film (MoN), WN, AlO film, TiO film, HfO film, ZrO film, TaO film, MoO, WO film, TiON film, TiAlCN film, TiAlC film, TiCN film, etc. on the wafer 200 through the above-mentioned processing sequence, the present invention can also be applied. In this method, the same effect as the above-mentioned method can be obtained.

[0218] In addition, in the above-mentioned embodiment, as a reactant, a gas containing N and H is used as an example. However, the present invention is not limited thereto. For example, a gas containing carbon (C) such as C2H4 gas, C2H2 gas, or C3H6 gas, a gas containing boron (B) such as B2H6 gas or BCl3 gas, oxygen (O2) gas, ozone (O3) gas, or plasma-excited O2 gas (O2 * ), O2 gas + hydrogen (H2) gas, water vapor (H2O gas), H2O2 gas, N2O gas, NO gas, NO2 gas, CO gas, CO2 gas and other gases containing oxygen (O). In addition, in this specification, the recording of two gases such as "O2 gas + H2 gas" refers to a mixed gas of H2 gas and O2 gas. When supplying a mixed gas, the two gases can be mixed (pre-mixed) in a supply pipe and then supplied to the processing chamber 201, or the two gases can be supplied to the processing chamber 201 from different supply pipes and mixed (post-mixed) in the processing chamber 201. As reactants, one or more of them can be used. In this method, the same effect as the above-mentioned method can be obtained.

[0219] In the above embodiment, an example of forming a SiN film on wafer 200 during substrate processing is described. However, the present invention is not limited thereto. In addition to SiN films, the present invention can also be applied to the formation of films containing Si, such as SiCN films, SiON films, SiOC films, SiOCN films, SiBCN films, SiBN films, and SiO films. This embodiment also achieves the same effects as the above embodiment.

[0220] In addition, in the above embodiment, the control unit is described as a physical controller (controller 121). However, the present invention is not limited to this. The control unit can also be stored in the memory of the controller in the form of a software program. In this embodiment, the same effect as the above embodiment can be obtained.

[0221] In addition, in the above-mentioned embodiment, the case where the gas supply system is composed of the first raw material supply system, the second raw material supply system, the reactant supply system, the first supply system, the second supply system, the inert gas supply system, and the controller 121 as the control unit described later is described as an example. However, the present invention is not limited to this. For example, the gas supply system may also be composed of the first raw material supply system, the second raw material supply system, the reactant supply system, the first supply system, the second supply system, the inert gas supply system, and a software program. It should be noted that the control unit may also be composed of a software program. In addition, the gas supply system is configured to be controlled so as to be able to perform the processing of the present invention.

[0222] The recipe for each treatment is preferably prepared separately according to the treatment content, and is pre-recorded and stored in the storage device 121c via a communication line or an external storage device 123. Furthermore, when each treatment is started, the CPU 121a preferably selects an appropriate recipe from the multiple recipes recorded and stored in the storage device 121c based on the treatment content. This allows a single substrate processing apparatus to reproducibly form films of various film types, composition ratios, film qualities, and film thicknesses. Furthermore, the burden on the operator is reduced, allowing each treatment to be started quickly while avoiding operational errors.

[0223] The above-mentioned recipes are not limited to newly created ones; for example, they can also be prepared by modifying an existing recipe already installed in a substrate processing apparatus. When modifying a recipe, the modified recipe can be installed in the substrate processing apparatus via a communication line or a recording medium containing the recipe. Alternatively, the existing recipe installed in the substrate processing apparatus can be modified directly by operating the input / output device 122 of the existing substrate processing apparatus.

[0224] In the above-described method, an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at a time is described. The present invention is not limited to the above-described method, and for example, it can also be appropriately applied to a case where a film is formed using a single-sheet substrate processing apparatus that processes one or more substrates at a time. In the above-described method, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace is described. The present invention is not limited to the above-described method, and it can also be appropriately applied to a case where a film is formed using a substrate processing apparatus having a cold-wall type processing furnace. In addition, in the above-described method, an example of activating a gas by heat is described. However, the present invention is not limited thereto. For example, when activating a gas by plasma generated inside or outside the processing chamber 201, or when activating a gas by irradiating the gas with electromagnetic waves using a lamp or the like, it can also be appropriately applied.

[0225] When these substrate processing apparatuses are used, each process can be performed using the same processing steps and processing conditions as those in the above-mentioned embodiment and modification examples, and the same effects as those in the above-mentioned embodiment and modification examples can be obtained.

[0226] The above-mentioned embodiments and modifications can be used in combination as appropriate. The processing steps and processing conditions in this case can be, for example, the same as those in the above-mentioned embodiments or modifications.

Claims

1. A substrate processing method comprising the step of forming a film on a substrate by performing a cycle comprising steps (a), (b), (c), and (d) a predetermined number of times, wherein: (a) is a step of supplying an inhibitor to a substrate; (b) a step of supplying a first raw material from a first storage portion to the substrate; (c) a step of supplying a second raw material from a second storage portion to the substrate; (d) is a step of supplying a reactant to the substrate.

2. The substrate processing method according to claim 1, wherein: (a) includes at least one of (a-1) supplying a first inhibitor to the substrate before (b) and (a-2) supplying a second inhibitor to the substrate before (c).

3. The substrate processing method according to claim 1, wherein: When performing (b), also perform (c), and when performing (c), perform (b).

4. The substrate processing method according to claim 2, wherein: When performing (b), also perform (c), and when performing (c), perform (b).

5. The substrate processing method according to claim 1, wherein: While performing (b), also perform (c).

6. The substrate processing method according to claim 2, wherein: While performing (b), also perform (c).

7. The substrate processing method according to claim 1, wherein: When performing (c), also perform (b).

8. The substrate processing method according to claim 2, wherein: When performing (c), also perform (b).

9. The substrate processing method according to claim 1, wherein: In (b), the first raw material stored in the first storage portion is supplied, In (c), the second raw material is supplied via the second storage portion.

10. The substrate processing method according to claim 2, wherein: In (b), the first raw material stored in the first storage portion is supplied, In (c), the second raw material is supplied via the second storage portion.

11. The substrate processing method according to claim 1, wherein: In (b), the first raw material is supplied via the first storage portion, In (c), the second raw material stored in the second storage section is supplied.

12. The substrate processing method according to claim 2, wherein: In (b), the first raw material is supplied via the first storage portion, In (c), the second raw material stored in the second storage section is supplied.

13. The substrate processing method according to claim 1, wherein: In (b), the first raw material stored in the first storage portion is supplied, In (c), the second raw material stored in the second storage section is supplied.

14. The substrate processing method according to claim 2, wherein: In (b), the first raw material stored in the first storage portion is supplied, In (c), the second raw material stored in the second storage section is supplied.

15. The substrate processing method according to claim 1, wherein: The first raw material and the second raw material are the same material.

16. The substrate processing method according to claim 1, wherein: The first raw material and the second raw material are different materials.

17. A method for manufacturing a semiconductor device, comprising the step of performing a cycle comprising steps (a), (b), (c), and (d) a predetermined number of times to form a film on a substrate, wherein: (a) is a step of supplying an inhibitor to a substrate; (b) a step of supplying a first raw material from a first storage portion to the substrate; (c) a step of supplying a second raw material from a second storage portion to the substrate; (d) is a step of supplying a reactant to the substrate.

18. A computer-readable recording medium recording a step of causing a substrate processing apparatus to execute, by a computer, a cycle comprising (a), (b), (c), and (d) a predetermined number of times to form a film on a substrate, wherein: (a) is a step of supplying an inhibitor to a substrate; (b) a step of supplying a first raw material from a first storage portion to the substrate; (c) a step of supplying a second raw material from a second storage portion to the substrate; (d) is a step of supplying a reactant to the substrate.

19. A substrate processing apparatus comprising: a first supply system for supplying an inhibitor to the substrate; A first raw material supply system is provided, which supplies a first raw material to the substrate; A second raw material supply system is provided, which supplies a second raw material to the substrate; a reactant supply system for supplying a reactant to the substrate; and A control unit configured to cause the first supply system, the first raw material supply system, the second raw material supply system, and the reactant supply system to execute a process of forming a film on the substrate by performing a cycle including (a), (b), (c), and (d) a predetermined number of times, wherein: (a) is a process of supplying the inhibitor to the substrate, (b) is a process of supplying the first raw material to the substrate, (c) is a process of supplying the second raw material to the substrate, and (d) is a process of supplying a reactant to the substrate.

20. A gas supply system comprising: a first supply system for supplying an inhibitor to the substrate; A first raw material supply system is provided, which supplies a first raw material to the substrate; A second raw material supply system is provided which includes a second storage portion and supplies a second raw material to the substrate; and a reactant supply system for supplying a reactant to the substrate; The gas supply system is controlled so as to be capable of performing a process of forming a film on the substrate by performing a cycle including (a), (b), (c), and (d) a predetermined number of times, wherein (a) is a process of supplying the inhibitor to the substrate, (b) is a process of supplying the first raw material to the substrate, (c) is a process of supplying the second raw material to the substrate, and (d) is a process of supplying a reactant to the substrate.

Images