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

Abstract

The present invention comprises: (a) a step for supplying a first processing gas to a substrate; (b) a step for heating the second process gas and storing the second process gas in a first storage unit; (c) a step for heating the second process gas and storing the second process gas in a second storage unit different from the first storage unit; (d) after (b), supplying the second processing gas to the substrate from the first storage part; and (e) a step of supplying the second processing gas to the substrate from the second storage unit after (c), and forming a film on the substrate by performing a predetermined number of times (f) and (g), where (f) is the step of performing (a) and (d), and (g) is the step of performing (a) and (e).

Description

Technical Field

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

[0002] As one of the steps in the process of manufacturing a semiconductor device, a process is sometimes performed in which a process gas is supplied to a plurality of substrates to form a film on each substrate (see, for example, Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2022-52622 Summary of the invention

[0006] Problems to be solved by the invention

[0007] It is desired to improve the properties of films formed on a plurality of substrates.

[0008] The present disclosure provides a technology capable of improving the characteristics of films formed on a plurality of substrates.

[0009] Means for solving problems

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

[0011] (a) supplying a first processing gas to a substrate;

[0012] (b) a step of heating the second process gas and storing the second process gas in the first storage portion;

[0013] (c) a step of heating the second process gas and storing the second process gas in a second storage portion different from the first storage portion;

[0014] (d) after step (b), supplying the second processing gas from the first storage unit to the substrate; and

[0015] (e) after step (c), supplying the second processing gas from the second storage unit to the substrate,

[0016] A film is formed on the substrate by performing (f) and (g) a predetermined number of times, wherein (f) is a step of performing (a) and (d), and (g) is a step of performing (a) and (e).

[0017] Effects of the Invention

[0018] According to the present disclosure, it is possible to improve the characteristics of films formed on a plurality of substrates. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and is a diagram showing a processing furnace 202 portion in a vertical cross-sectional view.

[0020] Figure 2 This is a schematic diagram of a vertical processing furnace of a substrate processing device preferably used in one embodiment of the present invention. Figure 1 The AA line cross-sectional view shows a portion of the processing furnace 202 .

[0021] 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 disclosure, and is a diagram showing a control system of the controller 121 in the form of a block diagram.

[0022] Figure 4 This is a diagram showing a processing sequence in one embodiment of the present disclosure.

[0023] Figure 5 This is a diagram showing a processing sequence in Modification Example 1. DETAILED DESCRIPTION

[0024] <One aspect of the present disclosure>

[0025] The following mainly refers to Figure 1 to Figure 4 One mode of the present disclosure is described. In addition, the drawings used in the following description are all schematic, and the dimensional relationship of each element, the ratio of each element, etc. shown in the drawings may not be consistent with the actual situation. In addition, the dimensional relationship of each element, the ratio of each element, etc. between multiple drawings may not be consistent.

[0026] (1) Structure of substrate processing apparatus

[0027] like Figure 1 As shown, the processing furnace 202 has a heater 207 as a temperature adjuster (heating unit). The heater 207 is cylindrical and is vertically mounted by being supported by a holding plate. The heater 207 also functions as an activation mechanism that activates the gas by heat.

[0028] On the inner side of the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS), and is formed into a cylindrical shape with an open upper end and a lower end. The upper end of the manifold 209 is engaged with the lower end of the reaction tube 203, and is configured to support the reaction tube 203. An O-ring 220a as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically like the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing container (reaction container). The processing chamber 201 is formed in the hollow portion of the cylinder of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. The wafer 200 is processed in the processing chamber 201 .

[0029] In the processing chamber 201, nozzles 249a and 249b as the first and second supply parts are respectively arranged in a manner penetrating the side wall of the manifold 209. The nozzles 249a and 249b are also referred to as the first and second nozzles, respectively. The nozzles 249a and 249b are made of a heat-resistant material such as quartz or SiC, for example. The nozzles 249a and 249b are connected to the gas supply pipes 232a and 232b, respectively. The nozzles 249a and 249b are different nozzles, and the nozzles 249a and 249b are respectively arranged adjacent to each other.

[0030] In the gas supply pipe 232a, a mass flow controller (MFC) 241a as a flow controller (flow control unit) and a valve 243a as an opening and closing valve are sequentially provided from the upstream side of the gas flow. In the gas supply pipe 232b, MFC241b, valve 243b1, tank 242b as a first storage unit, valve 243b2, and valve 612 are sequentially provided from the upstream side of the gas flow. The upstream end of the gas supply pipe 232c is connected to a position of the gas supply pipe 232b that is downstream of the MFC241b and upstream of the valve 243b1. In the gas supply pipe 232c, valve 243c1, tank 242c as a second storage unit, valve 243c2, and valve 622 are sequentially provided from the upstream side of the gas flow. The downstream end of the gas supply pipe 232c is connected to a position of the gas supply pipe 232b that is downstream of the valve 612. The vent pipe 610 may be connected to the gas supply pipe 232b at a position downstream of the valve 243b2 and upstream of the valve 612. The vent pipe 620 may be connected to the gas supply pipe 232c at a position downstream of the valve 243c2 and upstream of the valve 622. Valves 611 and 621 are provided on the vent pipes 610 and 620, respectively. The vent pipes 610 and 620 are connected to a position downstream of the APC valve 244 of the exhaust pipe 231 described later. The gas supply pipe 232d is connected to the gas supply pipe 232a at a position downstream of the valve 243a. The gas supply pipe 232e is connected to the gas supply pipe 232b at a position downstream of the valve 612. MFCs 241d and 241e and valves 243d and 243e are provided on the gas supply pipes 232d and 232e, respectively, in order from the upstream side of the gas flow. The gas supply pipes 232a to 232e and the vent pipes 610 and 620 are made of metal materials such as SUS. In addition, an example of providing one MFC 241b for each tank 242b and 242c is shown here, but the present invention is not limited thereto, and the gas supply system may be configured by providing one MFC for each tank 242b and 242c.

[0031] like Figure 2 As shown, in the annular space between the inner wall of the reaction tube 203 and the wafer 200 when viewed from above, nozzles 249a and 249b are respectively arranged in a manner of rising from the lower part of the inner wall of the reaction tube 203 along the upper part toward the arrangement direction of the wafer 200. That is, in the area on the side of the wafer arrangement area where the wafers 200 are arranged and horizontally surrounding the wafer arrangement area, nozzles 249a and 249b are respectively arranged in a manner along the wafer arrangement area. Gas supply holes 250a and 250b for supplying gas are respectively provided on the side of the nozzles 249a and 249b. The gas supply holes 250a and 250b are respectively opened toward the center of the wafer 200 when viewed from above, and can supply gas toward the wafer 200. A plurality of gas supply holes 250a and 250b are provided from the lower part to the upper part of the reaction tube 203.

[0032] The tanks 242b and 242c are configured as gas tanks or spiral pipes having a larger gas capacity than ordinary pipes. By opening and closing the valves 243b1 and 243c1 on the upstream side of the tanks 242b and 242c and the valves 243b2 and 243c2 on the downstream side, the gas supplied from the gas supply pipes 232b and 232c can be temporarily filled (stored) in the tanks 242b and 242c, respectively, and the gas temporarily stored in the tanks 242b and 242c can be supplied to the processing chamber 201.

[0033] By closing valves 243b2, 243c1, and 243c2 and opening valve 243b1, the gas whose flow rate has been adjusted by MFC241b can be temporarily stored in tank 242b. After a predetermined amount of gas is stored in tank 242b so that the pressure in tank 242b reaches a predetermined pressure, valve 243b1 is closed and valves 243b2 and 612 are opened, thereby the high-pressure gas stored in tank 242b can be supplied to processing chamber 201 at once (in a short time) through gas supply pipe 232b and nozzle 249b. In addition, by closing valves 243b1, 243b2, and 243c2 and opening valve 243c1, the gas whose flow rate has been adjusted by MFC241b can be temporarily stored in tank 242c. After a predetermined amount of gas is stored in the tank 242c so that the pressure in the tank 242c reaches a predetermined pressure, the valve 243c1 is closed and the valves 243c2 and 622 are opened, thereby the high-pressure gas stored in the tank 242c can be supplied to the processing chamber 201 at once (in a short time) through the gas supply pipes 232c, 232b and the nozzle 249b. In addition, by closing the valves 243b1 and 612 and opening the valves 243b2 and 611, the gas temporarily stored in the tank 242b can be exhausted to the exhaust pipe 231 through the vent pipe 610 without bypassing the processing chamber 201. In addition, by closing the valves 243c1 and 622 and opening the valves 243c2 and 621, the gas temporarily stored in the tank 242c can be exhausted to the exhaust pipe 231 through the vent pipe 620 without bypassing the processing chamber 201.

[0034] Heaters 242h1 and 242h2 are provided as first and second heating units for heating the tanks 242b and 242c, respectively, on the outer peripheries of the tanks 242b and 242c. By heating the tanks 242b and 242c with the heaters 242h1 and 242h2, the gas stored in the tanks 242b and 242c can be heated.

[0035] like Figure 1As shown by the middle dotted line, a belt-shaped heater 232h is wound around the outer periphery of the gas supply pipes 232b and 232c, for example, the outer periphery of the gas supply pipes 232b and 232c at the front section (upstream side) and the rear section (downstream side) of the tanks 242b and 242c, as a third heating unit for heating them. By heating the gas supply pipes 232b and 232c at the front section of the tanks 242b and 242c (for example, the gas supply pipes 232b and 232c from the MFC 241b to the primary side (inlet) of the tanks 242b and 242c) with the heater 232h, the gas supplied to the tanks 242b and 242c can be preheated. In addition, by using the heater 232h to heat the gas supply pipes 232b, 232c at the rear section of the tanks 242b, 242c (for example, the gas supply pipes 232b, 232c from the secondary side (outlet) of the tanks 242b, 242c to the processing chamber 201), the gas supplied from the tanks 242b, 242c to the processing chamber 201 can be heated.

[0036] A first process gas as a raw material is supplied from the gas supply pipe 232a via the MFC 241a, the valve 243a, and the nozzle 249a into the process chamber 201. The first process gas is used as one of the film-forming agents.

[0037] The second process gas as a reactant is supplied from the gas supply pipe 232b via the MFC 241b, the valve 243b1, the tank 242b, the valve 243b2, 612, and the nozzle 249b to the process chamber 201. In addition, the second process gas as a reactant is supplied from the gas supply pipe 232b via the MFC 241b, the gas supply pipe 232c, the valve 243c1, the tank 242c, the valve 243c2, 622, and the nozzle 249b to the process chamber 201. The second process gas is used as one of the film forming agents.

[0038] Inert gas is supplied from gas supply pipes 232d and 232e through MFCs 241d and 241e, valves 243d and 243e, gas supply pipes 232a and 232b, and nozzles 249a and 249b into the processing chamber 201. The inert gas functions as a purge gas, a carrier gas, a dilution gas, and the like.

[0039] The first supply system (raw material supply system) is mainly composed of a gas supply pipe 232a, MFC241a, and valve 243a. The second supply system (first reactant supply system) is mainly composed of a gas supply pipe 232b, MFC241b, valve 243b1, tank 242b, and valve 243b2. The third supply system (second reactant supply system) is mainly composed of a gas supply pipe 232c, valve 243c1, tank 242c, and valve 243c2. In addition, it is also possible to consider including the gas supply pipe 232b and MFC241b in the third supply system. The inert gas supply system is mainly composed of gas supply pipes 232d, 232e, MFC241d, 241e, valves 243d, and 243e. The first to third supply systems are also referred to as film-forming agent supply systems separately or in combination.

[0040] One or all of the various supply systems described above may be configured as an integrated supply system 248 that integrates valves 243a, 243b1, 243b2, 243c1, 243c2, 243d, 243e, 611, 612, 621, 622, MFCs 241a, 241b, 241d, etc. The integrated supply system 248 is configured such that: the integrated supply system 248 is connected to the gas supply pipes 232a to 232e, respectively, and the supply operation of various substances (various gases) into the gas supply pipes 232a to 232e is controlled by the controller 121 described later, that is, the opening and closing operation of the valves 243a, 243b1, 243b2, 243c1, 243c2, 243d, 243e, 611, 612, 621, 622, the flow rate adjustment operation of the MFCs 241a, 241b, 241d, etc. The integrated supply system 248 is constructed as an integrated unit of one piece or a split type, and can be loaded and unloaded relative to the gas supply pipes 232a to 232e as an integrated unit, and can be maintained, replaced, or expanded as an integrated unit.

[0041] An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided below the side wall of the reaction tube 203. Figure 2As shown in FIG. 1 , the exhaust port 231a is provided at a position facing (face to face) the nozzles 249a and 249b (gas supply holes 250a and 250b) across the wafer 200 in a top view. The exhaust port 231a can be provided from the lower part of the side wall of the reaction tube 203 along the upper part, that is, along the wafer arrangement area. The exhaust port 231a is connected to the exhaust pipe 231. The exhaust pipe 231 is connected to the vacuum pump 246 as a vacuum exhaust device via the pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and the APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit). The APC valve 244 is configured to: by opening and closing the valve in a state where the vacuum pump 246 is operated, the vacuum exhaust in the processing chamber 201 and the vacuum exhaust stop can be performed, and by adjusting the valve opening according to the pressure information detected by the pressure sensor 245 in a state where the vacuum pump 246 is operated, the pressure in the processing chamber 201 can be adjusted. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. It is also conceivable that a vacuum pump 246 is included in the exhaust system.

[0042] A sealing cover 219 as a furnace port cover body capable of hermetically closing the lower end opening of the manifold 209 is provided below 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 as a sealing member abutting against 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 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 lifted and lowered in the vertical direction by the wafer boat elevator 115 as a lifting mechanism provided outside the reaction tube 203. The boat elevator 115 is configured as a transport device (transport mechanism) that carries the wafer 200 into and out of the processing chamber 201 by raising and lowering the sealing cap 219 .

[0043] The wafer boat 217 as a substrate support is configured to support a plurality of wafers 200, for example, 25 to 200, in a horizontal posture and in a state where the centers of the wafers 200 are aligned with each other in a vertical direction in multiple stages, that is, arranged at intervals. The wafer boat 217 is made of a heat-resistant material such as quartz or SiC. A heat insulating portion 218 made of a heat-resistant material such as quartz or SiC is provided at the bottom of the wafer boat 217.

[0044] A temperature sensor 263 as a temperature detector is provided in the reaction tube 203. The power supply to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, so that the temperature in the processing chamber 201 has a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0045] 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) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. The controller 121 is connected to an input / output device 122 such as a touch panel. In addition, an external storage device 123 can be connected to the controller 121.

[0046] 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 actions of the substrate processing device, the process recipe that records the process and conditions of the substrate processing described later, etc., are recorded and stored in a readable manner in the storage device 121c. The process recipe is composed in a manner that the controller 121 can be used to enable the substrate processing device to execute each process in the substrate processing described later and obtain a specified result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are also collectively referred to as a program. In addition, the process recipe is also referred to as a process for short. When the term "program" is used in this specification, there is a case where only the process body is included, only the control program body is included, or both are included. RAM121b is configured as a storage area (work area) for temporarily holding programs, data, etc. read by CPU121a.

[0047] The I / O port 121d is connected to the above-mentioned MFC241a, 241b, 241d, valves 243a, 243b1, 243b2, 243c1, 243c2, 243d, 243e, 611, 612, 621, 622, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotating mechanism 267, wafer boat elevator 115, etc.

[0048] The CPU 121 a is configured to read out a control program from the storage device 121 c and execute the control program, and to read out a recipe from the storage device 121 c in response to input of an operation command from the input / output device 122 or the like. CPU121a is configured to control the flow adjustment action of various substances (various gases) based on MFC241a, 241b, and 241d, the opening and closing action of valves 243a, 243b1, 243b2, 243c1, 243c2, 243d, 243e, 611, 612, 621, and 622, the opening and closing action of APC valve 244 and the pressure adjustment action performed by APC valve 244 according to pressure sensor 245, the start and stop of vacuum pump 246, the temperature adjustment action of heater 207 according to temperature sensor 263, the rotation and rotation speed adjustment action of wafer boat 217 based on rotating mechanism 267, the lifting and lowering action of wafer boat 217 based on wafer boat elevator 115, etc. according to the read process content.

[0049] The controller 121 can be constructed by installing the above-mentioned program recorded and stored in the external storage device 123 on a computer. The external storage device 123 includes, for example, a disk such as an HDD, an optical disk such as a CD, an optical disk such as an MO, a semiconductor memory such as a USB memory, and an SSD. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, they are also collectively referred to as recording media. When the term recording medium is used in this specification, there is a case where only the storage device 121c monomer is included, a case where only the external storage device 123 monomer is included, or a case where both are included. In addition, 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 to the computer.

[0050] (2) Substrate processing steps

[0051] As one of the steps in the manufacturing process of a semiconductor device, the substrate processing apparatus described above is used, mainly Figure 4 A method of processing a substrate, that is, an example of a processing sequence for forming a film on a wafer 200 as a substrate will be described. In the following description, the operation of each unit constituting the substrate processing apparatus is controlled by the controller 121 .

[0052] The processing sequence in this method includes the following steps:

[0053] A step of supplying a first processing gas to the wafer 200 (step A);

[0054] A step of heating the second process gas and storing it in the tank 242b (step B);

[0055] A step of heating the second process gas and storing the second process gas in a tank 242c different from the tank 242b (step C);

[0056] After step B, a step of supplying a second process gas from the tank 242 b to the wafer 200 (step D); and

[0057] After step C, a step of supplying a second process gas from the tank 242c to the wafer 200 (step E) is performed.

[0058] A film is formed on the wafer 200 by performing a step (step F) of performing step A and step D and a step (step G) of performing step A and step E a predetermined number of times (n times, n being an integer greater than or equal to 1). Each step is performed in a non-plasma atmosphere.

[0059] In addition, Figure 4 In the example, for convenience, the implementation period of step A performed in step F is indicated as A1. Figure 4 In the example, for convenience, the implementation period of step A performed in step G is represented as A2. Figure 4 In the embodiment, for convenience, the implementation periods of steps B to G are respectively indicated as B to G. Figure 4 In the embodiment, for convenience, tanks 242b and 242c are respectively indicated as T1 and T2. The implementation period of each step and the description of each tank are shown in the gas supply sequence of the modified example described later. Figure 5 The same is true in Chinese.

[0060] In addition, in the following example, Figure 4 , an example of performing a cycle including step F and step G a plurality of times is shown.

[0061] 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, other aspects, etc.

[0062] [(first process gas → T1: second process gas) → (first process gas → T2: second process gas)] × n

[0063] The term "wafer" used in this specification may refer to the wafer itself or a stack of a wafer and a predetermined layer or film formed on its surface. The term "surface of the wafer" used in this specification may refer to the surface of the wafer itself or the surface of a predetermined layer, etc. formed on the wafer. When the term "a predetermined layer is formed on the wafer" is recorded in this specification, it may refer to directly forming a predetermined layer on the surface of the wafer itself or forming a predetermined layer on a layer, etc. formed on the wafer. The use of the term "substrate" in this specification is synonymous with the use of the term "wafer".

[0064] The term "agent" 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, a film-forming agent (raw material, reactant) may include a gaseous substance, a liquid substance such as a mist substance, or both.

[0065] The term "layer" used in this specification includes at least one of a continuous layer and a discontinuous layer. The layer formed in each step described below may include a continuous layer, a discontinuous layer, or both.

[0066] (Wafer loading and wafer boat loading)

[0067] When a plurality of wafers 200 are loaded into the wafer boat 217 (wafer loading), as shown in FIG. Figure 1 As 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 loading). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b. In this way, the wafers 200 are prepared in the processing chamber 201.

[0068] (Pressure adjustment and temperature adjustment)

[0069] After the wafer boat is loaded, vacuum exhaust (decompression exhaust) is performed by the vacuum pump 246, so that the space in the processing chamber 201, that is, the space where the wafer 200 is located, becomes the desired pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback controlled based on the measured pressure information. In addition, the heater 207 is used to heat the wafer 200 in the processing chamber 201 so that the desired processing temperature is reached. At this time, the power supply to the heater 207 is feedback controlled based on the temperature information detected by the temperature sensor 263, so that the desired temperature distribution is achieved in the processing chamber 201. In addition, the rotation of the wafer 200 by the rotating mechanism 267 is started. 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.

[0070] (Step of charging gas into storage unit)

[0071] In this step, the following two steps, namely, steps B and C, are implemented.

[0072] [Step B]

[0073] In this step, the second process gas is heated and stored in the tank 242b.

[0074] Specifically, in the state of closing valves 243b2, 243c1, and 243c2, valve 243b1 is opened to allow the second process gas to flow into the gas supply pipe 232b. The second process gas is flow-adjusted by MFC241b, supplied to the tank 242b, and stored in the tank 242b. At this time, the gas supply pipe 232b from MFC241b to the inlet of the tank 242b is heated to a specified temperature by the heater 232h, and the second process gas supplied to the tank 242b is preheated. After the second process gas of a specified pressure and a specified amount is stored in the tank 242b, valve 243b1 is closed, and the second process gas is sealed (sealed) in the tank 242b. At this time, the tank 242b is heated to a specified temperature by the heater 242h1, and the second process gas stored in the tank 242b is heated. The volume of the tank 242b is preferably 300 to 2000cc, for example. In this case, it is preferred that the pressure in the tank 242b when the second process gas is sealed in the tank 242b is set to a high pressure of, for example, 20000Pa or more, and it is desirable that the amount of the second process gas stored in the tank 242b (the amount at elevated temperature and normal pressure) is set to, for example, 120 to 3000cc, preferably 120 to 2000cc. Through this series of actions, the storage action (filling action) of the second process gas in the tank 242b is completed (the gas in the first storage unit is charged).

[0075] By heating the second process gas stored in the tank 242b, the preheated second process gas can be supplied to the wafer 200 in step D described later. In addition, by preheating the second process gas supplied to the tank 242b, the temperature of the second process gas can be stabilized in the tank 242b. As a result, in step D described later, the second process gas whose temperature is stabilized can be supplied to the wafer 200. These points are also the same in step C described later.

[0076] This step is a preliminary preparation for performing step D described later.

[0077] [Step C]

[0078] In this step, the second process gas is heated and stored in the tank 242c.

[0079] Specifically, in the state where valves 243b1, 243b2, and 243c2 are closed, valve 243c1 is opened to allow the second process gas to flow into gas supply pipes 232b and 232c. The second process gas is flow-adjusted by MFC241b, supplied to tank 242c, and stored in tank 242c. At this time, the gas supply pipes 232b and 232c from MFC241b to the inlet of tank 242c are heated to a predetermined temperature by heater 232h, and the second process gas supplied to tank 242c is preheated. After the second process gas of a predetermined pressure and a predetermined amount is stored in tank 242c, valve 243c1 is closed, and the second process gas is sealed (sealed) in tank 242c. At this time, tank 242c is heated to a predetermined temperature by heater 242h2, and the second process gas stored in tank 242c is heated. The volume of tank 242c is set to the same volume as tank 242b. Through this series of operations, the storage operation (filling operation) of the second process gas into the tank 242c is completed (charging of the gas into the second storage unit).

[0080] This step is a preliminary preparation for performing step E described later.

[0081] (Film Forming Step)

[0082] The following first and second film forming steps are performed in sequence.

[0083] [First film forming step]

[0084] In the first film forming step (hereinafter also referred to as step F), the following steps A1 and D are performed alternately and asynchronously.

[0085] [Step A1]

[0086] In this step, a first process gas, that is, a raw material (raw material gas) as a film-forming agent is supplied to the wafer 200 .

[0087] Specifically, valve 243a is opened to allow the raw material to flow into gas supply pipe 232a. The raw material is flow-regulated by MFC 241a, supplied into processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, the raw material is supplied to wafer 200 from the side of wafer 200 (raw material supply). At this time, valves 243d and 243e may also be opened to supply inert gas into processing chamber 201 via nozzles 249a and 249b, respectively.

[0088] As the processing conditions when the raw material is supplied in step A, the following are exemplified:

[0089] Processing temperature: 300~550℃

[0090] Processing pressure: 1~3990Pa

[0091] Raw material supply flow rate: 0.1~2.0slm

[0092] Inert gas supply flow rate (per gas supply pipe): 0.1~20slm

[0093] Each gas supply time: 1 to 70 seconds, preferably 5 to 20 seconds.

[0094] In addition, the numerical range expression such as "300-550°C" in this specification means that the lower limit and the upper limit are included in the range. Therefore, for example, "300-550°C" means "above 300°C and below 550°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, when the supply flow rate includes 0slm, 0slm means that the substance (gas) is not supplied. These are the same in the following descriptions.

[0095] Step A1 is performed under the above-mentioned processing conditions, and a gas containing, for example, titanium halide is supplied to the wafer 200 as a raw material, thereby forming a titanium (Ti)-containing layer containing halogen on the wafer 200. In this specification, the Ti-containing layer containing halogen is also referred to as a Ti-containing layer. In addition, the Ti-containing layer formed in step A1 is also referred to as a first Ti-containing layer.

[0096] After the first Ti-containing layer is formed on the wafer 200, the valve 243a is closed to stop supplying the raw material into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove the gaseous substances remaining in the processing chamber 201 from the processing chamber 201. At this time, the valves 243d and 243e are opened, and an inert gas is supplied into the processing chamber 201 through the nozzles 249a and 249b. The inert gas supplied from the nozzles 249a and 249b acts as a purge gas, thereby purging the processing chamber 201. The processing temperature during the purge in this step is preferably set to the same temperature as the processing temperature during the supply of the raw material.

[0097] As a raw material, for example, a Ti-containing gas containing titanium (Ti) as the first element constituting the film formed on the wafer 200 can be used. As a Ti-containing gas, for example, a substance that also contains at least one halogen element of chlorine (Cl), F, bromine (Br), and iodine (I), that is, a gas containing a halide (titanium halide) can be used. As a gas containing a titanium halide, for example, a chlorotitanium-based gas containing Ti and Cl can be used. As a chlorotitanium-based gas, for example, titanium dichloride (TiCl2) gas, titanium tetrachloride (TiCl4) gas, titanium trichloride (TiCl3) gas, etc. can be used. As a raw material, in addition to the chlorotitanium-based gas, a titanium fluoride-based gas such as titanium tetrafluoride (TiF4) can also be used. As a raw material, one or more of them can be used.

[0098] As the inert gas, rare gases such as nitrogen (N2), argon (Ar), helium (He), neon (Ne), and xenon (Xe) can be used. As the inert gas, one or more of them can be used. This is also the same in each step described later.

[0099] After the first Ti-containing layer is formed, step C for implementing step E described later is started. At this time, step C may be started without exhausting the atmosphere in tank 242c. That is, a predetermined amount of gas may be accumulated in tank 242c from before step C is started. Figure 4 As shown by the dotted line in the middle, the tank 242c may be vented and step C may be started during the first execution of step A1. Figure 4 The storage sequence of T2 of the first cycle shown is the same as the storage of the second cycle and the Nth cycle.

[0100] [Step D]

[0101] After step A1 is completed, the second process gas as a film-forming agent stored in the tank 242 b is supplied to the wafer 200 , that is, to the wafer 200 after the first Ti-containing layer is formed.

[0102] Here, an example in which a nitriding agent (nitriding gas) containing nitrogen as a second element different from the first element is used as the second process gas will be described. This also applies to step E described later.

[0103] Specifically, while valves 243b1, 243c1, and 243c2 are closed, valves 243b2 and 612 are opened to allow the high-pressure nitriding agent stored in tank 242b to flow into processing chamber 201 at once through gas supply pipe 232b and nozzle 249b. Thus, nitriding agent is supplied to wafer 200 at once (flash supply). At this time, gas supply pipe 232b from the outlet of tank 242b to processing chamber 201 is heated to a predetermined temperature by heater 232h to suppress the temperature drop of nitriding agent supplied into processing chamber 201. In addition, valves 243d and 243e may be opened at this time to supply inert gas into processing chamber 201 through nozzles 249a and 249b, respectively. Flash supply is performed in any state from a state where the exhaust system is substantially fully closed (APC valve 244 is substantially fully closed) to a state where it is fully opened. Here, substantially closed (substantially fully closed) includes a state where the APC valve 244 is vacant by about 0.1 to several %, and a state where exhaust is discharged into the exhaust system even if the APC valve 244 is controlled to be 100% closed due to the performance of the APC valve 244 .

[0104] After a predetermined time has passed since the start of the flash supply, the valves 243b2 and 612 are maintained open, and the valve 243b1 is opened. The nitriding agent is flow-regulated by the MFC241b and supplied to the processing chamber 201 via the gas supply pipe 232b, the tank 242b, and the nozzle 249b. Thus, the nitriding agent is supplied to the wafer 200 (non-flash supply). Thus, in the non-flash supply of the nitriding agent, the nitriding agent is supplied to the processing chamber 201 without pre-storing the nitriding agent in the tank 242b. In this case, the speed of the nitriding agent on the wafer 200 is also lower than that in the case of flash supply. At this time, the gas supply path from the MFC241b to the processing chamber 201, that is, the gas supply pipe 232b and the tank 242b, is heated to a predetermined temperature by the heaters 232h and 242h1, so as to preheat the nitriding agent supplied to the processing chamber 201. In addition, at this time, the valves 243d and 243e may be opened to supply the inert gas into the processing chamber 201 through the nozzles 249a and 249b, respectively. In order to make the pressure in the processing chamber 201 reach a predetermined value during the non-flash supply of the nitriding agent, the APC valve 244 is not set to a fully closed state, but is set to a state between fully open and fully closed, for example.

[0105] As the treatment conditions when the nitriding agent is supplied in step D, the following are exemplified:

[0106] Processing temperature: 300~550℃

[0107] Processing pressure (flash supply): 1~3990Pa

[0108] Processing pressure (non-flash supply): 1~3990Pa

[0109] Nitriding agent supply flow rate: 0.1~30slm

[0110] Inert gas supply flow rate (per gas supply pipe): 0.1~30slm

[0111] Nitriding agent supply time (flash supply): 1 to 10 seconds

[0112] Nitriding agent supply time (non-flash supply): 1 to 120 seconds.

[0113] Step D is performed under the above-mentioned processing conditions, and a nitriding agent is supplied to the wafer 200, thereby generating a substitution reaction between at least a portion of the first Ti-containing layer formed on the wafer 200 in step A1 and the nitriding agent. During the substitution reaction, Ti contained in the first Ti-containing layer is bonded to nitrogen (N) contained in the nitriding agent, and a first titanium nitride layer (first TiN layer) is formed on the wafer 200 as a layer containing Ti and N. That is, the nitriding agent is supplied to the wafer 200 under the above-mentioned processing conditions, thereby forming a first TiN layer in which the first Ti-containing layer is nitrided (modified) on the wafer 200. When the first TiN layer is formed, impurities such as halogens contained in the first Ti-containing layer constitute a gaseous substance containing at least halogens during the substitution reaction (modification reaction) of the first Ti-containing layer based on the nitriding agent, and are discharged from the processing chamber 201. As a result, the first TiN layer becomes a layer with less impurities such as halogens than the first Ti-containing layer formed in step A1. This is also the same in step E described later.

[0114] In step D, when the nitriding agent is flash-supplied to the wafer 200, the nitriding agent is pre-stored in the tank 242b and supplied to the processing chamber 201 after being heated. That is, the pre-heated nitriding agent is supplied to the wafer 200. In addition, when the nitriding agent is flash-supplied and non-flash-supplied to the wafer 200, the nitriding agent is pre-heated in the nitriding agent supply path and then supplied to the processing chamber 201. As a result, the reaction between the first Ti-containing layer and the nitriding agent can be started under uniform conditions in the entire area of ​​the wafer arrangement area, such as a uniform heating state of the nitriding agent. As a result, the uniformity between the wafer surfaces (film thickness uniformity, film quality uniformity, etc.) can be improved. In addition, by supplying the pre-heated nitriding agent to the wafer 200, the reactivity of the first Ti-containing layer and the nitriding agent can be improved, and their reaction can be promoted. As a result, the thickness uniformity and step coverage of the first TiN layer formed on the wafer 200 within the wafer surface can be improved. In addition, the concentration of impurities such as halogens in the first TiN layer can be reduced. By reducing the impurity concentration in the first TiN layer, a film with a lower resistivity can be obtained. In addition, by supplying the nitriding agent whose temperature is stabilized in step B to the wafer 200, the reaction between the first Ti-containing layer and the nitriding agent can be started under more uniform conditions in the entire region of the wafer arrangement area. As a result, the uniformity between wafer surfaces can be reliably improved. These points are also the same in step E described later.

[0115] In addition, in step D, when the nitriding agent is initially supplied to the wafer 200, the nitriding agent is pre-stored in the tank 242b and then supplied to the processing chamber 201. That is, a large amount of nitriding agent is supplied at one time (flash supply) in a very short time. At this time, compared with the case where the nitriding agent is supplied to the processing chamber 201 without being pre-stored in the tank 242b (non-flash supply), more nitriding agent can be supplied to the surface of the wafer 200 located in the upper side (Top region) of the wafer arrangement direction of the wafer arrangement region. In addition, in step D, after the nitriding agent is flash-supplied to the wafer 200, non-flash supply is performed. In this case, compared with flash supply, more nitriding agent can be supplied to the surface of the wafer 200 located in the lower side (Bottom region) of the wafer arrangement direction of the wafer arrangement region. In this way, in step D, by performing flash supply and non-flash supply of the nitriding agent, the amount of nitriding agent supplied to the inter-surface of the wafer 200 can be made uniform in the entire region of the wafer arrangement region. As a result, the uniformity between the wafer surfaces can be more reliably improved. This is also the case in step E described later.

[0116] After the first Ti-containing layer formed on the wafer 200 is nitrided and changed (converted) into the first TiN layer, the valves 243b1, 243b2, and 612 are closed to stop the supply of the nitriding agent into the processing chamber 201. Then, by the same processing process and processing conditions as those in the purge in step A1, the gaseous substances and the like remaining in the processing chamber 201 are removed (purged) from the processing chamber 201. The processing temperature during the purge in this step is preferably set to the same temperature as the processing temperature during the supply of the nitriding agent.

[0117] As the nitriding agent, for example, a nitrogen (N)-containing gas such as a hydrogen nitride gas can be used. As the hydrogen nitriding gas, for example, an ammonia (NH3) gas can be used. As the nitriding agent, in addition to NH3 gas, hydrogen nitriding gases such as diazene (N2H2) gas and hydrazine (N2H4) gas can also be used. As the nitriding agent, one or more of them can be used. This is also the same in step E described later.

[0118] [Second film forming step]

[0119] In the second film forming step (hereinafter also referred to as step G), the following steps A2 and E are performed alternately and asynchronously.

[0120] [Step A2]

[0121] In this step, the first process gas, ie, the raw material (raw material gas), is supplied to the wafer 200, ie, the first TiN layer formed on the wafer 200. The process and process conditions in step A2 are the same as those in step A1.

[0122] Step A2 is performed under the above-mentioned processing conditions, and a gas containing, for example, titanium halide is supplied as a raw material to the wafer 200, thereby forming a Ti-containing layer on the outermost surface of the wafer 200, that is, on the first TiN layer formed on the wafer 200, as in step A1. The Ti-containing layer formed in step A2 is also referred to as a second Ti-containing layer.

[0123] After the second Ti-containing layer is formed, the supply of the raw material into the processing chamber 201 is stopped by the same process as step A1. Then, the gaseous substances and the like remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 by the same process and process conditions as those in the purging in step A1. The processing temperature during purging in this step is preferably set to the same temperature as the processing temperature during the supply of the raw material.

[0124] After the second Ti-containing layer is formed, step B for implementing step D in the next cycle is started. At this time, step B may be started without exhausting the atmosphere in tank 242b. In other words, step B may be started while the atmosphere in tank 242b is retained. That is, step B may be started while gas remains in tank 242b. By starting step B while the atmosphere in tank 242b is retained, the amount of gas supplied to tank 242b can be reduced. That is, the storage time in tank 242b can be reduced. This process is the same for tank 242c.

[0125] [Step E]

[0126] After step A2 is completed, the second process gas, ie, the nitriding agent, stored in the tank 242 c is supplied to the wafer 200 , ie, to the wafer 200 after the second Ti-containing layer is formed.

[0127] Specifically, while the valves 243b1, 243b2, and 243c1 are closed, the valves 243c2 and 622 are opened, so that the high-pressure nitriding agent stored in the tank 242c flows into the processing chamber 201 at one go through the gas supply pipes 232c, 232b, and the nozzle 249b. Thus, the nitriding agent is supplied to the wafer 200 at one go (flash supply). At this time, the gas supply pipes 232b and 232c from the outlet of the tank 242c to the processing chamber 201 are heated to a predetermined temperature by the heater 232h, so that the temperature drop of the nitriding agent supplied into the processing chamber 201 is suppressed. After a predetermined time has passed since the start of the flash supply, the valves 243c2 and 622 are maintained open, and the valve 243c1 is opened. The nitriding agent is supplied into the processing chamber 201 via the gas supply pipes 232b and 232c, the tank 242c, and the nozzle 249b with the flow rate adjusted by the MFC 241b. Thus, the nitriding agent is supplied to the wafer 200 (non-flash supply). At this time, the gas supply path from the MFC 241b to the processing chamber 201, that is, the gas supply pipes 232b, 232c, and the tank 242c are heated to a predetermined temperature by the heaters 232h and 242h2 to preheat the nitriding agent supplied to the processing chamber 201. The other processing procedures are the same as those in step D. The processing conditions in this step are the same as those in step D.

[0128] Step E is performed under the above-described processing conditions, and a nitriding agent is supplied to the wafer 200 , thereby forming a second TiN layer in which at least a portion of the second Ti-containing layer formed on the wafer 200 in step A2 is nitrided (modified).

[0129] After the second Ti-containing layer formed on the wafer 200 is nitrided and changed (converted) into the second TiN layer, the valves 243c1, 243c2, and 622 are closed to stop the supply of the nitriding agent into the processing chamber 201. Then, by the same processing process and processing conditions as those in the purge in step A1, the gaseous substances and the like remaining in the processing chamber 201 are removed (purged) from the processing chamber 201. The processing temperature during the purge in this step is preferably set to the same temperature as the processing temperature during the supply of the nitriding agent.

[0130] [Number of times the regulations are implemented]

[0131] The cycle of performing the above-mentioned step F and step G alternately and asynchronously is performed for a predetermined number of times (n times, where n is an integer greater than 1), thereby forming a titanium nitride film (TiN film) having a predetermined film thickness and composed of a stacked film in which a first TiN layer and a second TiN layer are alternately stacked on the wafer 200. The above-mentioned cycle is preferably repeated a plurality of times. That is, it is preferred that the thickness of the stacked film formed in each cycle is made thinner than the desired film thickness, and the above-mentioned cycle is repeated a plurality of times until the film thickness of the film formed by stacking the stacked films reaches the desired film thickness.

[0132] In addition, as described above, in step A1, after the first Ti-containing layer is formed, step C for performing step E is started. In addition, as described above, in step A2, after the second Ti-containing layer is formed, step B for performing step D in the next cycle is started. By alternately performing step F and step G, that is, alternately using tanks 242b and 242c to supply the nitriding agent, at least a part of step B and at least a part of step C can be performed in parallel. As a result, the retention time of the nitriding agent in tanks 242b and 242c, that is, the heating time, can be ensured to be a predetermined time. In addition, the cycle time can be shortened, and productivity can be improved.

[0133] In addition, by alternately using the tanks 242b and 242c to supply the nitriding agent, step C can be performed in parallel with a portion of step F, and step B can be performed in parallel with a portion of step G. Figure 4 In FIG. 1 , step C is performed in parallel with step D which is a part of step F, and step B is performed in parallel with step E which is a part of step G. Figure 4 , an example is shown in which step D is started after step C is started, and step E is started after step B is started. Thus, the residence time of the nitriding agent in the tanks 242b and 242c, that is, the heating time, can be sufficiently ensured.

[0134] (Post-Purge and Atmospheric Pressure Restoration)

[0135] After a TiN film of a desired thickness is formed on the wafer 200, an inert gas as a purge gas is supplied from the nozzles 249a and 249b to the process chamber 201, and the gas is exhausted from the exhaust port 231a. Thus, the process chamber 201 is purged, and the gas, reaction byproducts, etc. remaining in the process chamber 201 are removed from the process chamber 201 (post-purge). At this time, the valves 243b2, 243c2, 611, 612, 621, and 622 are opened, and the nitriding agent remaining in the tanks 242b and 242c is exhausted to the exhaust pipe 231 via the process chamber 201 and the vent pipes 610 and 620. After that, the atmosphere in the process chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the process chamber 201 is restored to normal pressure (atmospheric pressure restoration).

[0136] (Wafer boat unloading and wafer unloading)

[0137] After that, the sealing cover 219 is lowered by the wafer boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafers 200 are carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the wafer boat 217 (wafer boat unloading). After being carried out to the outside of the reaction tube 203, the processed wafers 200 are taken out of the wafer boat 217 (wafer unloading).

[0138] (3) Effects of this method

[0139] According to this aspect, one or more of the following effects can be obtained.

[0140] (a) In steps D and E, by supplying the preheated nitriding agent to the wafer 200, the reaction between the first Ti-containing layer and the second Ti-containing layer formed on the wafer 200 and the nitriding agent can be started under uniform conditions in the entire wafer arrangement region. As a result, the uniformity (film thickness uniformity, film quality uniformity, etc.) between wafer surfaces can be improved.

[0141] (b) In steps D and E, by supplying the preheated nitriding agent to the wafer 200, the reactivity of the first Ti-containing layer and the second Ti-containing layer formed on the wafer 200 with the nitriding agent can be improved, and their reaction can be promoted. As a result, the characteristics of the film formed on the wafer 200 can be improved. For example, the thickness uniformity and step coverage of the first TiN layer and the second TiN layer formed on the wafer 200 within the wafer surface can be improved. In addition, the impurity concentration in the first TiN layer and the second TiN layer can be reduced, and the first TiN layer and the second TiN layer can be made into a high-quality film with higher conductivity (low resistivity).

[0142] (c) By alternately performing step F and step G, that is, by alternately using tanks 242b and 242c to supply the nitriding agent, at least a portion of step B and at least a portion of step C can be performed in parallel. Thus, the residence time of the nitriding agent in tanks 242b and 242c, that is, the heating time, can be ensured to be a predetermined time.

[0143] (d) By alternately using the tanks 242b and 242c to supply the nitriding agent, step C can be performed in parallel with a portion of step F, and step B can be performed in parallel with a portion of step G. Thus, the residence time of the nitriding agent in the tanks 242b and 242c, that is, the heating time, can be sufficiently ensured.

[0144] (e) The gas supply pipes 232b and 232c from the MFC 241b to the respective inlets of the tanks 242b and 242c are heated to a predetermined temperature by the heater 232h, and the nitriding agent supplied to the tanks 242b and 242c is preheated, thereby stabilizing the temperature of the nitriding agent in the tanks 242b and 242c. Thus, in steps D and E, the temperature-stabilized nitriding agent can be supplied to the wafer 200. As a result, the reaction of the first Ti-containing layer and the second Ti-containing layer with the nitriding agent can be started under more uniform conditions in the entire region of the wafer arrangement region, and the uniformity between wafer surfaces can be reliably improved.

[0145] (f) The above-mentioned effect can also be obtained when a predetermined substance (gaseous substance, liquid substance) is arbitrarily selected from the above-mentioned various raw materials, various reactants, and various inert gases. In addition, the above-mentioned effect can also be obtained when the halogen contained in the first processing gas is any one of Cl, F, Br, and I.

[0146] (4) Modification

[0147] The substrate processing sequence in this embodiment can be changed as shown in the following modified examples. These modified examples can be combined arbitrarily. Unless otherwise specified, the processing process and processing conditions in each step of each modified example can be the same as the processing process and processing conditions in each step of the above-mentioned substrate processing sequence.

[0148] (Variant 1)

[0149] like Figure 5 As shown in the processing sequence, after forming the first TiN layer in step D, the preparation for step D in the next cycle, i.e., step B, may be performed from before step G (step A2) starts to before step D in step F in the next cycle starts. Alternatively, after forming the second TiN layer in step E, the preparation for step E in the next cycle, i.e., step C, may be performed from before step F (step A1) starts to before step E in step G in the next cycle starts. Figure 5The following example is represented: after the first TiN layer is formed in step D, preparation for step D in the next cycle, i.e., step B, is started, and step B is performed before step D in the next cycle is started; after the second TiN layer is formed in step E, preparation for step E in the next cycle, i.e., step C, is started, and step C is performed before step E in the next cycle is started.

[0150] In this modification, the same effects as those of the above embodiment can be obtained. In addition, according to this modification, the retention time of the nitriding agent in the tanks 242b and 242c, that is, the heating time, can be more sufficiently ensured. As a result, the temperature of the nitriding agent in the tanks 242b and 242c can be reliably stabilized.

[0151] (Variant 2)

[0152] After the supply of the nitriding agent in step D is completed, that is, after the first TiN layer is formed, the atmosphere in the tank 242b may be exhausted to discharge the nitriding agent remaining in the tank 242b. In addition, after the supply of the nitriding agent in step E is completed, that is, after the second TiN layer is formed, the atmosphere in the tank 242c may be exhausted to discharge the nitriding agent remaining in the tank 242c. Specifically, after the supply of the nitriding agent in steps D and E is completed and before the start of steps B and C for the next steps D and E, the atmospheres in the tanks 242b and 242c may be exhausted, respectively.

[0153] Specifically, while the valves 243b1, 243c1, 612, and 622 are closed, the valves 243b2, 243c2, 611, and 621 are opened to discharge the nitriding agent remaining in the tanks 242b and 242c from the vent pipes 610 and 620 without passing through the process chamber 201 (without passing through the process chamber 201). Alternatively, while the valves 243b1 and 243c1 are closed, the valves 243b2, 243c2, 612, and 622 are opened to discharge the nitriding agent remaining in the tanks 242b and 242c from the exhaust pipe 231 through the process chamber 201 (through the process chamber 201). Alternatively, exhaust without passing through the process chamber 201, that is, exhaust from the vent pipes 610 and 620 and exhaust through the process chamber 201, may be performed. In this case, it is preferable to perform exhaust from the vent pipes 610 and 620 after exhausting the process chamber 201. In this case, exhaust from the vent pipes 610 and 620 and exhausting the process chamber 201 may be performed in parallel. It is preferable to perform exhaust from the vent pipes 610 and 620 during the implementation of step A2 performed after step D is completed or during the implementation of step A1 performed after step E is completed. In addition, when the wafer 200 is present in the process chamber 201, it is preferable to perform exhaust of the atmosphere in the tanks 242b and 242c through the vent pipes 610 and 620.

[0154] This can reduce the amount of the nitriding agent decomposed in the tanks 242 b and 242 c . As a result, the amount of the nitriding agent supplied to the wafer 200 can be made uniform in each cycle.

[0155] (Variant 3)

[0156] In the case where the heaters 242h1 and 242h2 are provided, the heater 232h may not be provided. That is, the heaters 242h1 and 242h2 may be used to heat the tanks 242b and 242c, respectively, and the second process gas supplied to the processing chamber 201 may be preheated in steps D and E. In this modified example, in steps D and E, a preheated nitriding agent may be supplied to the wafer 200, and the same effect as the above method may be obtained. As described above, the heater 232h is preferably provided in that the second process gas supplied to the tanks 242b and 242c may be preheated and the second process gas supplied from the tanks 242b and 242c to the processing chamber 201 may be heated.

[0157] (Variant 4)

[0158] In the case where the heater 232h is provided, the heaters 242h1 and 242h2 may not be provided. That is, in steps B and C, the gas supply pipes 232b and 232c may be heated to a predetermined temperature by the heater 232h, and in steps D and E, the second process gas supplied to the process chamber 201 may be preheated. In this modified example, in steps D and E, a preheated nitriding agent may be supplied to the wafer 200, and the same effect as the above-mentioned method may be obtained. As described above, in order to heat the second process gas in the tanks 242b and 242c and stabilize the temperature of the second process gas, it is preferable to provide the heaters 242h1 and 242h2.

[0159] (Variant 5)

[0160] The heater 232h may be at least provided in the front section of the tanks 242b and 242c of the gas supply pipes 232b and 232c. In this modification, in steps B and C, the second processing gas supplied to the tanks 242b and 242c may also be heated. As a result, in steps D and E, the preheated nitriding agent may be supplied to the wafer 200, and the same effect as the above method may be obtained. In addition, in this modification, the second processing gas supplied to the tank 242b may also be preheated. As a result, in this modification, when the heaters 242h1 and 242h2 are provided, the temperature of the second processing gas may also be stabilized in the tanks 242b and 242c.

[0161] (Variant 6)

[0162] In step F, at least a portion of the implementation period of the above-mentioned step A1 and at least a portion of the implementation period of step D may be repeated. In addition, in step G, at least a portion of the implementation period of the above-mentioned step A2 and at least a portion of the implementation period of step E may be repeated. That is, the first processing gas and the second processing gas may be simultaneously supplied to the wafer 200 as film forming agents. In this modified example, the same effect as the above method can also be obtained.

[0163] (Variant 7)

[0164] In steps D and E, the non-flash supply of the nitriding agent may be omitted. In this modified example, the same effect as in the above-mentioned method can be obtained. However, as described above, in steps D and E, the non-flash supply of the nitriding agent is preferably performed after the flash supply of the nitriding agent, in order to make the amount of the nitriding agent supplied to the surfaces of the wafer 200 uniform over the entire area of ​​the wafer arrangement region and to more reliably improve the uniformity between the wafer surfaces.

[0165] (Variant 8)

[0166] The number of tanks as the storage unit for storing the second process gas is not limited to two, and can be arbitrarily set to three or more. In addition, when there are three or more tanks, the storage and supply of the nitriding agent are performed cyclically using three or more tanks. That is, the "alternation" in the present disclosure includes the case where three or more tanks are used cyclically.

[0167] <Other aspects of the present disclosure>

[0168] The embodiments of the present disclosure have been specifically described above. However, the present disclosure is not limited to the above embodiments, and various modifications can be made without departing from the spirit thereof.

[0169] For example, the present disclosure can also be applied to the case where a film containing semiconductor elements such as silicon (Si) and germanium (Ge), zirconium (Zr), hafnium (Hf), tantalum (Ta), aluminum (Al), molybdenum (Mo), tungsten (W), ruthenium (Ru) and other metal elements as the first element is formed on a substrate. The processing process and processing conditions when supplying the film-forming agent can be the same as the processing process and processing conditions in each step of the above method. In these cases, the same effects as the above method can be obtained.

[0170] For another example, the present disclosure can also be applied to the case of forming a film containing an element such as oxygen (O), carbon (C), nitrogen (N), or boron (B) as a second element on a substrate. For example, the present disclosure can also be applied to the following situations: as reactants, the above-mentioned nitrogen-containing gas, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, hydrogen (H2) gas + oxygen (O2) gas, ozone (O3) gas and other oxygen-containing gases, ethylene (C2H4) gas, acetylene (C2H2) gas, propylene (C3H6) gas and other carbon-containing gases, triethylamine ((C2H5)3N) gas, trimethylamine ((CH3)3N) gas and other nitrogen and carbon-containing gases, diborane (B2H6) gas, trichloroborane (BCl3) gas and other boron-containing gases are used, and through the above-mentioned processing sequence, titanium oxide film (TiO film), titanium oxycarbide film (TiOC film), titanium oxycarbonitride film (TiOCN film), titanium nitride carbide film (TiCN film), titanium nitride boride film (TiBN film), titanium nitride carbon boride film (TiBCN film), etc. are formed on the substrate. The process and conditions for supplying the film-forming agent may be the same as those in the steps of the above-mentioned method. In these cases, the same effects as those of the above-mentioned method can be obtained.

[0171] In addition, in this specification, "H2 gas + O2 gas" means a mixed gas of H2 gas and O2 gas. When supplying a mixed gas, the two gases can be mixed in a supply pipe (premixed) 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 in the processing chamber 201 (postmixed).

[0172] Preferably, the process used in each treatment is prepared separately according to the treatment content, recorded and stored in the storage device 121c via the electrical communication line and the external storage device 123. In addition, preferably, when starting each treatment, the CPU 121a appropriately selects a suitable process from the multiple processes recorded and stored in the storage device 121c according to the treatment content. Thus, a film of various film types, composition ratios, film qualities, and film thicknesses can be formed with good reproducibility using one substrate processing device. In addition, the burden on the operator can be reduced, operational errors can be avoided, and each treatment can be started quickly.

[0173] The above process is not limited to the case of new production, and can also be prepared by, for example, changing an existing process already installed in a substrate processing device. When changing a process, the changed process can be installed in the substrate processing device via an electrical communication line or a recording medium recording the process. In addition, the input / output device 122 of the existing substrate processing device can be operated to directly change the existing process already installed in the substrate processing device.

[0174] In the above-mentioned method, an example of forming a film using a batch-type substrate processing device that processes a plurality of substrates at a time is described. The present disclosure is not limited to the above-mentioned method, and for example, it can also be appropriately applied when a film is formed using a single-piece substrate processing device that processes one or more substrates at a time. In addition, in the above-mentioned method, an example of forming a film using a substrate processing device having a hot-wall type processing furnace is described. The present disclosure is not limited to the above-mentioned method, and it can also be appropriately applied when a film is formed using a substrate processing device having a cold-wall type processing furnace.

[0175] When these substrate processing apparatuses are used, each process can be performed with the same process procedures and process conditions as those of the above-mentioned embodiments and modified examples, and the same effects as those of the above-mentioned embodiments and modified examples can be obtained.

[0176] The above-mentioned forms and modified examples can be used in combination as appropriate. The processing process and processing conditions in this case may be the same as those of the above-mentioned forms and modified examples, for example.

[0177] Explanation of symbols

[0178] 200 wafers (substrates).

Claims

1. A substrate processing method, characterized in that: It has the following processes: (a) supplying a first processing gas to a substrate; (b) a step of heating the second process gas and storing the second process gas in the first storage portion; (c) a step of heating the second process gas and storing the second process gas in a second storage portion different from the first storage portion; (d) after step (b), supplying the second processing gas from the first storage unit to the substrate; and (e) after step (c), supplying the second processing gas from the second storage unit to the substrate, A film is formed on the substrate by performing (f) and (g) a predetermined number of times, wherein (f) is a step of performing (a) and (d), and (g) is a step of performing (a) and (e).

2. The substrate processing method according to claim 1, characterized in that: At least a portion of (b) and at least a portion of (c) are performed in parallel.

3. The substrate processing method according to claim 1, characterized in that: After starting (c), proceed to (d). After starting (b), proceed to (e).

4. The substrate processing method according to claim 1, characterized in that: The substrate processing method further comprises the following steps: (h) after the supply of the second process gas in (d) is completed, the step of exhausting the atmosphere in the first storage unit; as well as (i) After the supply of the second process gas in (e) is completed, a step of exhausting the atmosphere in the second storage unit.

5. The substrate processing method according to claim 4, characterized in that: In (h) and (i), respectively, exhaust is performed through the space where the substrate is located and exhaust is performed without passing through the space.

6. The substrate processing method according to claim 1, characterized in that: Repeat several cycles involving (f) and (g). After performing (d), starting (b) without exhausting the atmosphere in the first storage unit, After (e) is performed, (c) is started without exhausting the atmosphere in the second storage section.

7. The substrate processing method according to claim 1, characterized in that: Repeat several cycles involving (f) and (g). performing (c) in parallel with at least a portion of (f), (b) is performed in parallel with at least a portion of (g).

8. The substrate processing method according to claim 7, characterized in that: From the time (f) starts until the time (e) of the next step (g) starts, do (c), Perform (b) from before the start of (g) to before the start of (d) in the next (f).

9. The substrate processing method according to claim 1, characterized in that: The second processing gas in (b) is heated by a first heating unit provided in the first storage unit, The second processing gas in (c) is heated by a second heating unit provided in the second storage unit.

10. The substrate processing method according to claim 9, characterized in that: The second process gas in (b) and (c) is heated by a third heating unit provided in front of the first storage unit and the second storage unit.

11. The substrate processing method according to claim 1, characterized in that: The second process gas in (b) and (c) is heated by a third heating unit provided in front of the first storage unit and the second storage unit.

12. A method for manufacturing a semiconductor device, characterized in that: It has the following processes: (a) supplying a first processing gas to a substrate; (b) a step of heating the second process gas and storing the second process gas in the first storage portion; (c) a step of heating the second process gas and storing the second process gas in a second storage portion different from the first storage portion; (d) after step (b), supplying the second processing gas from the first storage unit to the substrate; and (e) after step (c), supplying the second processing gas from the second storage unit to the substrate, A film is formed on the substrate by performing (f) and (g) a predetermined number of times, wherein (f) is a step of performing (a) and (d), and (g) is a step of performing (a) and (e).

13. A substrate processing device, characterized in that: have: a processing chamber that processes the substrate; a first supply system for supplying a first processing gas to the substrate in the processing chamber; a second supply system for supplying a second processing gas stored in the first storage portion to the substrate in the processing chamber; a third supply system for supplying a second processing gas stored in a second storage portion different from the first storage portion to the substrate in the processing chamber; a first heating part that heats the first storage part; a second heating portion that heats the second storage portion; and The control unit is configured to control the first supply system, the second supply system, the third supply system, the first heating unit, and the second heating unit so that the following processing is performed in the processing chamber: (a) supplying a first processing gas to the substrate; (b) heating the second process gas and storing the second process gas in the first storage portion; (c) heating the second process gas and storing the second process gas in the second storage portion; (d) after (b), supplying the second process gas from the first reservoir to the substrate; and (e) after (c), supplying the second processing gas from the second storage unit to the substrate, A film is formed on the substrate by performing (f) and (g) a predetermined number of times, wherein (f) is a process of performing (a) and (d), and (g) is a process of performing (a) and (e).

14. A program, characterized in that The computer enables the substrate processing device to perform the following process: (a) supplying a first processing gas to a substrate; (b) heating the second process gas and storing it in the first storage portion; (c) heating the second process gas and storing the second process gas in a second storage portion different from the first storage portion; (d) after step (b), supplying the second processing gas from the first storage unit to the substrate; (e) after step (c), supplying the second process gas from the second storage unit to the substrate; and A process of forming a film on the substrate by performing (f) and (g) a predetermined number of times, wherein (f) is the process of performing (a) and (d), and (g) is the process of performing (a) and (e).

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