JP2019054291A - Semiconductor device manufacturing method, substrate processing apparatus and program - Google Patents

Abstract

To inhibit generation of particles when a film is formed on a substrate.SOLUTION: A semiconductor device manufacturing method comprises a step of forming a film on a substrate by non-simultaneously performing predetermined times a cycle which includes : a step of supplying a material gas to the substrate in a processing chamber; a step of discharging the material gas from the processing chamber; a step of supplying an oxygen-containing gas to the substrate in the processing chamber; a step of discharging the oxygen-containing gas from the processing chamber; a step of supplying a hydrogen-containing gas to the substrate in the processing chamber; and a step of discharging the hydrogen-containing gas from the processing chamber. At least either of an effect or efficiency of gas discharge is made higher than that or those in the step of discharging the material gas.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method of manufacturing a semiconductor device, a substrate processing apparatus, and a program.

  A film is formed on a substrate by supplying a source gas, an oxygen (O) -containing gas, and a hydrogen (H) -containing gas non-simultaneously to a substrate in a processing chamber as one step of a manufacturing process of a semiconductor device (device). Process may be performed.

  However, the inventors of the present invention have made it clear by intensive research that, if O-containing gas or H-containing gas is supplied into the processing chamber, a large amount of particles may be generated in the processing chamber. An object of the present invention is to provide a technology capable of suppressing the generation of particles when forming a film on a substrate.

According to one aspect of the invention:
Supplying a source gas to the substrate in the processing chamber;
Discharging the source gas from the processing chamber;
Supplying an oxygen-containing gas to the substrate in the processing chamber;
Discharging the oxygen-containing gas from the processing chamber;
Supplying a hydrogen-containing gas to the substrate in the processing chamber;
Discharging the hydrogen-containing gas from the processing chamber;
Forming a film on the substrate by performing a predetermined number of non-simultaneous cycles.
A method of manufacturing a semiconductor device, wherein at least one of the gas discharging effect and the efficiency in the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas is larger than that in the step of discharging the source gas Is provided.

  According to the present invention, it is possible to suppress the generation of particles when forming a film on a substrate.

It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus suitably used by one Embodiment of this invention, and is a figure which shows a processing furnace part by a longitudinal cross-sectional view. It is a schematic block diagram of the vertical processing furnace of the substrate processing apparatus suitably used by one Embodiment of this invention, and is a figure which shows a processing furnace part by the sectional view on the AA line of FIG. It is a schematic block diagram of the controller of the substrate processing apparatus suitably used by one Embodiment of this invention, and is a figure which shows the control system of a controller with a block diagram. It is a figure which shows the timing change of the gas supply in the film-forming sequence of one Embodiment of this invention, and the pressure change in a processing chamber, and a mode that the time of purge processing was lengthened in each step which discharges O containing gas and H containing gas is shown. FIG. It is a figure which shows the timing change of the gas supply in the film-forming sequence of one Embodiment of this invention, and the pressure change in a process chamber, and a mode that the supply flow rate of purge gas was enlarged in each step which discharges O containing gas and H containing gas. FIG. It is a figure which shows the pressure change in the timing of gas supply in the film-forming sequence of one Embodiment of this invention, and a processing chamber, In each step which discharges O containing gas and H containing gas, evacuation processing and purge processing are sequentially It is a figure which shows a mode that it carries out. It is a figure which shows the timing of gas supply in the film-forming sequence of one Embodiment of this invention, In each step which discharges O containing gas and H containing gas, the cycle purge process which repeats vacuum suction processing and purge processing alternately is performed. It is a figure which shows a mode that it carries out. It is a figure which shows the modification 1-7 of the film-forming sequence of one Embodiment of this invention. It is a figure which shows the modification 8-10 of the film-forming sequence of one Embodiment of this invention. It is a figure which shows the modification 11-13 of the film-forming sequence of one Embodiment of this invention. It is a figure which shows the modification 14-16 of the film-forming sequence of one Embodiment of this invention. It is a figure which illustrates the film-forming sequence of other embodiment of this invention. (A) is a figure which shows the chemical structural formula of HCDS, (b) shows the chemical structural formula of OCTS. (A) is a figure which shows the chemical structural formula of BTCSM, (b) shows the chemical structural formula of BTCSE. (A) shows the chemical structural formula of TCDMDS, (b) shows the chemical structural formula of DCTMDS, (c) shows the chemical structural formula of MCPMDS. (A) is a schematic block diagram of the processing furnace of the substrate processing apparatus suitably used by other embodiment of this invention, is a figure which shows a processing furnace part by a longitudinal cross-sectional view, (b) is other things of this invention It is a schematic block diagram of the processing furnace of the substrate processing apparatus suitably used by this embodiment, and is a figure which shows a processing furnace part by a longitudinal cross-sectional view.

<One embodiment of the present invention>
Hereinafter, an embodiment of the present invention will be described using FIGS. 1 to 3.

(1) Configuration of Substrate Processing Apparatus As shown in FIG. 1, the processing furnace 202 has a heater 207 as a heating unit (heating mechanism). The heater 207 has a cylindrical shape and is vertically installed by being supported by a heater base (not shown) as a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that thermally activates (excites) the gas as described later.

Inside the heater 207, a reaction tube 203 which constitutes a reaction container (processing container) concentrically with the heater 207 is disposed. The reaction tube 203 is made of, for example, a heat resistant material such as quartz (SiO ₂ ) or silicon carbide (SiC), and is formed in a cylindrical shape whose upper end is closed and whose lower end is open. A processing chamber 201 is formed in the hollow portion of the reaction tube 203. The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate in a state in which the wafers 200 are horizontally aligned and vertically aligned in multiple stages by a boat 217 described later.

  In the processing chamber 201, a nozzle 249a as a first nozzle and a nozzle 249b as a second nozzle are provided so as to penetrate the lower side wall of the reaction tube 203. The nozzles 249a and 249b are made of, for example, a heat resistant material such as quartz or SiC. Gas supply pipes 232a and 232b are connected to the nozzles 249a and 249b, respectively. As described above, the reaction tube 203 is provided with two nozzles 249a and 249b and two gas supply tubes 232a and 232b, and can supply a plurality of types of gas into the processing chamber 201. It has become.

  However, the processing furnace 202 of this embodiment is not limited to the above-mentioned form. For example, a metal manifold supporting the reaction tube 203 may be provided below the reaction tube 203, and each nozzle may be provided so as to penetrate the side wall of the manifold. In this case, an exhaust pipe 231 described later may be further provided in the manifold. Even in this case, the exhaust pipe 231 may be provided at the lower part of the reaction pipe 203 instead of the manifold. As described above, the furnace port of the processing furnace 202 may be made of metal, and a nozzle or the like may be attached to the metal furnace port.

  In the gas supply pipes 232a and 232b, mass flow controllers (MFC) 241a and 241b, which are flow controllers (flow control units), and valves 243a and 243b, which are on-off valves, are provided in this order from the upstream direction. Gas supply pipes 232c and 232d for supplying an inert gas are connected to the gas supply pipes 232a and 232b at the downstream side of the valves 243a and 243b, respectively. The gas supply pipes 232c and 232d are provided with MFCs 241c and 241d, which are flow controllers (flow control units), and valves 243c and 243d, which are on-off valves, in this order from the upstream direction.

  Nozzles 249a and 249b are connected to tip end portions of the gas supply pipes 232a and 232b, respectively. The nozzles 249a and 249b are, as shown in FIG. 2, in an annular space between the inner wall of the reaction tube 203 and the wafer 200, along the upper portion from the lower portion of the inner wall of the reaction tube 203, It is provided to stand up to each. That is, the nozzles 249a and 249b are provided along the wafer array area in the area horizontally surrounding the wafer array area on the side of the wafer array area in which the wafers 200 are arrayed. That is, the nozzles 249 a and 249 b are respectively provided on the sides (edges) of the end portion (peripheral portion) of the wafer 200 carried into the processing chamber 201 perpendicularly to the surface (flat surface) of the wafer 200. The nozzles 249a and 249b are respectively configured as L-shaped long nozzles, and their respective horizontal portions are provided to penetrate the lower side wall of the reaction tube 203, and their respective vertical portions are at least arranged in a wafer arrangement. It is provided to rise from one end side to the other end side of the region. Gas supply holes 250a and 250b for supplying gas are respectively provided on side surfaces of the nozzles 249a and 249b. The gas supply holes 250 a and 250 b are opened to face the center of the reaction tube 203, and can supply gas toward the wafer 200. A plurality of gas supply holes 250a and 250b are provided from the lower portion to the upper portion of the reaction tube 203, each having the same opening area, and further provided at the same opening pitch.

  Thus, in the present embodiment, an annular longitudinally long space defined by the inner wall of the side wall of the reaction tube 203 and the end (peripheral portion) of the plurality of wafers 200 arranged in the reaction tube 203. The gas is transported via the nozzles 249a and 249b disposed inside, that is, in the cylindrical space. Then, gas is ejected from the gas supply holes 250 a and 250 b opened in the nozzles 249 a and 249 b into the reaction tube 203 for the first time near the wafer 200. Then, the main flow of the gas in the reaction tube 203 is in the direction parallel to the surface of the wafer 200, ie, in the horizontal direction. With such a configuration, the gas can be uniformly supplied to each wafer 200, and the film thickness uniformity of the thin film formed on each wafer 200 can be improved. The gas that has flowed over the surface of the wafer 200, that is, the residual gas after reaction flows toward the exhaust port, that is, the exhaust pipe 231 described later. However, the direction of the flow of the residual gas is appropriately specified by the position of the exhaust port, and is not limited to the vertical direction.

  From the gas supply pipe 232a, as a source gas having a predetermined element, for example, a halosilane source gas containing Si and a halogen element as the predetermined element is supplied into the processing chamber 201 via the MFC 241a, the valve 243a and the nozzle 249a. .

  The halosilane source gas is a gaseous halosilane source, for example, a gas obtained by vaporizing a halosilane source which is liquid at normal temperature and pressure, or a halosilane source which is gaseous at normal temperature and pressure. The halosilane raw material is a silane raw material having a halogen group. The halogen group includes a chloro group, a fluoro group, a bromo group, an iodo group and the like. That is, the halogen group includes halogen elements such as chlorine (Cl), fluorine (F), bromine (Br) and iodine (I). The halosilane raw material can be said to be a kind of halide. When the term "raw material" is used in the present specification, when "liquid raw material in liquid state" is meant, "raw material gas in gaseous state" is meant, or when both are meant. is there.

As the halosilane source gas, for example, a C-free source gas containing Si and Cl, that is, an inorganic chlorosilane source gas can be used. As the inorganic chlorosilane source gas, for example, hexachlorodisilane (Si ₂ Cl ₆ , abbreviation: HCDS) gas, octachlorotrisilane (Si ₃ Cl ₈ , abbreviation: OCTS) gas, or the like can be used. FIG. 13 (a) shows the chemical structural formula of HCDS, and FIG. 13 (b) shows the chemical structural formula of OCTS. These gases contain at least two Si in one molecule, further contain Cl, and can be said to be source gases having Si-Si bonds. These gases act as Si sources in the substrate processing step described later.

Further, as the halosilane source gas, for example, a source gas containing Si, Cl and an alkylene group and having a Si-C bond, that is, an alkylene chlorosilane source gas which is an organic chlorosilane source gas can also be used. The alkylene group includes a methylene group, an ethylene group, a propylene group, a butylene group and the like. The alkylene chlorosilane source gas can also be referred to as an alkylene halosilane source gas. As the alkylene chlorosilane source gas, for example, bis (trichlorosilyl) methane ((SiCl ₃ ) ₂ CH ₂ , abbreviation: BTCSM) gas, ethylene bis (trichlorosilane) gas, that is, 1,2-bis (trichlorosilyl) ethane ((SiCl ₃ ) ₂ C ₂ H ₄ , abbreviation: BTCSE) gas or the like can be used. FIG. 14 (a) shows the chemical structural formula of BTCSM, and FIG. 14 (b) shows the chemical structural formula of BTCSE. These gases contain at least two Si in one molecule, further contain C and Cl, and can be said to be source gases having Si-C bonds. These gases also act as Si sources and also act as C sources in the substrate processing step described later.

Further, as the halosilane source gas, for example, a source gas containing Si, Cl and an alkyl group and having a Si-C bond, that is, an alkylchlorosilane source gas which is an organic chlorosilane source gas can also be used. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group and the like. The alkyl chlorosilane source gas can also be referred to as an alkyl halosilane source gas. As the alkylchlorosilane source gas, for example, 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH ₃ ) ₂ Si ₂ Cl ₄ , abbreviation: TCDMDS) gas, 1,2-dichloro-1 1,2,2-Tetramethyldisilane ((CH ₃ ) ₄ Si ₂ Cl ₂ , abbreviation: DCTMDS) gas, 1-monochloro-1,1,2,2,2-pentamethyldisilane ((CH ₃ ) ₅ Si ₂ Cl, abbreviated: MCPMDS) gas or the like can be used. Fig. 15 (a) shows the chemical structural formula of TCDMDS, Fig. 15 (b) shows the chemical structural formula of DCTMDS, and Fig. 15 (c) shows the chemical structural formula of MCPMDS. These gases contain at least two Si in one molecule, further contain C and Cl, and can be said to be source gases having Si-C bonds. These gases also have Si-Si bonds. These gases also act as Si sources and also act as C sources in the substrate processing step described later.

  When using a liquid material that is in a liquid state at normal temperature and normal pressure such as HCDS, BTCSM, TCDMDS, etc., the material in the liquid state is vaporized by a vaporization system such as a vaporizer or bubbler, and the source gas (HCDS gas, BTCSM gas, etc.) is used. , TCDMDS gas etc.).

Further, a carbon (C) -containing gas, for example, is supplied from the gas supply pipe 232a to the processing chamber 201 through the MFC 241a, the valve 243a and the nozzle 249a as a reaction gas having a chemical structure different from that of the source gas. As C containing gas, hydrocarbon system gas can be used, for example. The hydrocarbon-based gas is also a substance composed of only two elements of C and H, and acts as a C source in the substrate processing step described later. As a hydrocarbon gas, for example, propylene (C ₃ H ₆ ) gas can be used.

Further, from the gas supply pipe 232b, for example, an oxygen (O) -containing gas is supplied into the processing chamber 201 through the MFC 241b, the valve 243b and the nozzle 249b as a reaction gas having a chemical structure different from that of the source gas. The O-containing gas acts as an oxidizing gas, that is, an O source in a substrate processing step described later. As the O-containing gas, for example, oxygen (O ₂ ) gas can be used.

  Further, a hydrogen (H) -containing gas, for example, is supplied from the gas supply pipe 232b to the processing chamber 201 through the MFC 241b, the valve 243b, and the nozzle 249b as a reaction gas having a chemical structure different from that of the source gas.

As the H-containing gas, for example, a hydrogen nitride-based gas which is a gas containing nitrogen (N) and hydrogen (H) can be used. The hydrogen nitride-based gas can also be referred to as a nitrogen (N) -containing gas, even though it is a substance composed of only two elements of N and H. The N-containing gas acts as a nitriding gas, that is, an N source in a substrate processing step described later. For example, ammonia (NH ₃ ) gas can be used as the hydrogen nitride-based gas.

Further, as the H-containing gas, for example, an amine-based gas which is a gas containing N, C and H can also be used. The amine-based gas may be a substance composed of only three elements of C, N and H, and may be referred to as a gas containing N and C. The amine-based gas also acts as an N source and also acts as a C source in the substrate processing step described later. As an amine-based gas, for example, triethylamine ((C ₂ H ₅ ) ₃ N, abbreviation: TEA) gas can be used. When using an amine that is in a liquid state at normal temperature and pressure as in TEA, the amine in the liquid state is vaporized by a vaporization system such as a vaporizer or a bubbler, and is supplied as an amine-based gas (TEA gas).

Further, as the H-containing gas, for example, an organic hydrazine gas which is a gas containing N, C and H can also be used. The organic hydrazine gas can be referred to as a gas containing N and C, even though it is a substance composed of only three elements of C, N and H. The organic hydrazine gas also acts as an N source and also acts as a C source in the substrate processing step described later. As the organic hydrazine gas, for example, trimethylhydrazine ((CH ₃ ) ₂ N ₂ (CH ₃ ) H, abbreviation: TMH) gas can be used. When using an amine that is in a liquid state at normal temperature and normal pressure as in TMH, the amine in the liquid state is vaporized by a vaporization system such as a vaporizer or bubbler and supplied as an organic hydrazine gas (TMH gas) .

Further, as the H-containing gas, for example, a gas containing no N or C such as hydrogen (H ₂ ) gas or deuterium (D ₂ ) gas can also be used.

From the gas supply pipes 232c and 232d, for example, nitrogen (N ₂ ) gas as an inert gas is respectively processed through the MFCs 241c and 241d, the valves 243c and 243d, the gas supply pipes 232a and 232b, and the nozzles 249a and 249b. 201 is supplied.

  When the source gas is supplied from the gas supply pipe 232a, a source gas supply system is mainly configured by the gas supply pipe 232a, the MFC 241a, and the valve 243a. The nozzle 249a may be included in the source gas supply system. The source gas supply system can also be referred to as a source supply system. When the halosilane source gas is supplied from the gas supply pipe 232a, the source gas supply system can also be referred to as a halosilane source gas supply system or a halosilane source supply system.

  When the C-containing gas is supplied from the gas supply system 232a, the C-containing gas supply system is mainly configured by the gas supply pipe 232a, the MFC 241a, and the valve 243a. The nozzle 249a may be included in the C-containing gas supply system. When a hydrocarbon-based gas is supplied from the gas supply pipe 232a, the C-containing gas supply system can also be referred to as a hydrocarbon-based gas supply system or a hydrocarbon supply system.

  When the O-containing gas is supplied from the gas supply system 232b, the O-containing gas supply system is mainly configured by the gas supply pipe 232b, the MFC 241b, and the valve 243b. The nozzle 249 b may be included in the O-containing gas supply system. The O-containing gas supply system can also be referred to as an oxidizing gas supply system or an oxidant supply system.

  When the H-containing gas is supplied from the gas supply pipe 232b, an H-containing gas supply system is mainly configured by the gas supply pipe 232b, the MFC 241b, and the valve 243b. The nozzle 249 b may be included in the H-containing gas supply system. When a gas containing N and H is supplied from the gas supply pipe 232b, the H-containing gas supply system can also be referred to as an N-containing gas supply system, a gas supply system containing N and H, or the like. When a gas containing N, C and H is supplied from the gas supply pipe 232b, the H-containing gas supply system is referred to as an N-containing gas supply system, a C-containing gas supply system, a gas supply system containing N and C, etc. It can also be done. The N-containing gas supply system can also be referred to as a nitriding gas supply system or a nitriding agent supply system. When a hydrogen nitride gas, an amine gas, or an organic hydrazine gas is supplied as the H-containing gas, the H-containing gas supply system may be a hydrogen nitride gas supply system, an amine gas supply system, an organic hydrazine gas supply system, etc. It can be called.

  Any or all of the C-containing gas supply system, the O-containing gas supply system, and the H-containing gas supply system described above may be referred to as a reactive gas supply system or a reactant supply system.

  In addition, an inert gas supply system is mainly configured by the gas supply pipes 232c and 232d, the MFCs 241c and 241d, and the valves 243c and 243d. The inert gas supply system can also be referred to as a purge gas supply system, a dilution gas supply system, or a carrier gas supply system.

  The reaction pipe 203 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201. The exhaust pipe 231 is provided with a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit). The vacuum pump 246 as an evacuation apparatus is connected. The APC valve 244 can perform vacuum evacuation and vacuum evacuation stop inside the processing chamber 201 by opening and closing the valve while operating the vacuum pump 246, and further, with the vacuum pump 246 operating, By adjusting the valve opening based on the pressure information detected by the pressure sensor 245, the pressure in the processing chamber 201 can be adjusted. An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

  Below the reaction tube 203, a seal cap 219 as a furnace port cover capable of airtightly closing the lower end opening of the reaction tube 203 is provided. The seal cap 219 is configured to abut on the lower end of the reaction tube 203 from the lower side in the vertical direction. The seal cap 219 is made of metal such as SUS, for example, and formed in a disk shape. On the top surface of the seal cap 219, an O-ring 220 is provided as a seal member that abuts on the lower end of the reaction tube 203. On the opposite side of the processing chamber 201 of the seal cap 219, a rotation mechanism 267 for rotating a boat 217 described later is installed. The rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217 through the seal cap 219. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be vertically lifted and lowered by a boat elevator 115 as a lift mechanism vertically installed outside the reaction tube 203. The boat elevator 115 is configured to be able to carry the boat 217 into and out of the processing chamber 201 by moving the seal cap 219 up and down. That is, the boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers the boat 217, that is, the wafer 200 into and out of the processing chamber 201.

  The boat 217 as a substrate support supports a plurality of, for example, 25 to 200 wafers 200 in a horizontal posture and vertically aligned with the centers aligned with one another, that is, It is configured to arrange at intervals. The boat 217 is made of, for example, a heat resistant material such as quartz or SiC. At the lower part of the boat 217, a heat insulating plate 218 made of a heat resistant material such as quartz or SiC is supported in multiple stages in a horizontal posture. This configuration makes it difficult for the heat from the heater 207 to be transmitted to the seal cap 219 side. However, this embodiment is not limited to the above-mentioned form. For example, without providing the heat insulating plate 218 in the lower part of the boat 217, a heat insulating cylinder configured as a cylindrical member made of a heat resistant material such as quartz or SiC may be provided.

  In the reaction tube 203, a temperature sensor 263 as a temperature detector is installed. By adjusting the degree of energization of the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature in the processing chamber 201 becomes a desired temperature distribution. The temperature sensor 263 is configured in an L-shape similar to the nozzles 249a and 249b, and is provided along the inner wall of the reaction tube 203.

  As shown in FIG. 3, the controller 121, which is a control unit (control means), is configured as a computer including a central processing unit (CPU) 121a, a random access memory (RAM) 121b, a storage device 121c, and an I / O port 121d. It is done. 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 the internal bus 121e. An input / output device 122 configured as, for example, a touch panel or the like is connected to the controller 121.

  The storage device 121 c is configured by, for example, a flash memory, a hard disk drive (HDD), or the like. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, and a process recipe in which a procedure, conditions and the like of the substrate processing described later are stored are readably stored. The process recipe is a combination of processes so as to cause the controller 121 to execute each procedure in the substrate processing process described later and obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the control program and the like are collectively referred to simply as a program. When the term "program" is used in the present specification, it may include only a process recipe alone, may include only a control program alone, or may include both of them. The RAM 121 b is configured as a memory area (work area) in which programs and data read by the CPU 121 a are temporarily stored.

  The I / O port 121d is connected to the MFCs 241a to 241d, the valves 243a to 243d, the pressure sensor 245, the APC valve 244, the vacuum pump 246, the heater 207, the temperature sensor 263, the rotation mechanism 267, the boat elevator 115, etc. .

  The CPU 121a is configured to read out and execute a control program from the storage device 121c, and to read out a process recipe from the storage device 121c in response to an input of an operation command from the input / output device 122 or the like. The CPU 121a adjusts the flow rates of various gases by the MFCs 241a to 241d, opens and closes the valves 243a to 243d, opens and closes the APC valve 244, and pressure from the APC valve 244 based on the pressure sensor 245 so as to follow the contents of the read process recipe. Adjustment operation, start and stop of vacuum pump 246, temperature adjustment operation of heater 207 based on temperature sensor 263, rotation and rotation speed adjustment of boat 217 by rotation mechanism 267, elevation operation of boat 217 by boat elevator 115, etc. are controlled. Is configured as.

  The controller 121 is not limited to being configured as a dedicated computer, and may be configured as a general-purpose computer. For example, an external storage device storing the above program (for example, a magnetic disk, a magnetic disk such as a flexible disk or hard disk, an optical disk such as a CD or DVD, a magnetooptical disk such as MO, a semiconductor memory such as a USB memory or memory card) The controller 121 according to the present embodiment can be configured by preparing the program 123 and using the external storage device 123 to install a program in a general-purpose computer. However, the means for supplying the program to the computer is not limited to the case of supplying via the external storage device 123. For example, the program may be supplied using communication means such as the Internet or a dedicated line without using the external storage device 123. The storage device 121 c and the external storage device 123 are configured as computer readable recording media. Hereinafter, these are collectively referred to simply as recording media. When the term "recording medium" is used in the present specification, when only the storage device 121c is included, or when only the external storage device 123 is included, or both of them may be included.

(2) Substrate Processing Process As an example of a process of manufacturing a semiconductor device (device) using the above-described substrate processing apparatus, a sequence example of forming a film on a substrate will be described with reference to FIGS. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

In the film forming sequence shown in FIGS.
Supplying HCDS gas as a source gas to the wafer 200 as a substrate in the processing chamber 201;
Step 1p of discharging HCDS gas from the inside of the processing chamber 201;
Supplying a C ₃ H ₆ gas as a C-containing gas to the wafer 200 in the processing chamber 201;
Step 2p of discharging C ₃ H ₆ gas from inside of the processing chamber 201,
Supplying an O ₂ gas as an O-containing gas to the wafer 200 in the processing chamber 201;
Step 3p of discharging O ₂ gas from inside of the processing chamber 201;
Supplying NH ₃ gas as H-containing gas to the wafer 200 in the processing chamber 201;
Step 4p of discharging the NH ₃ gas from the inside of the processing chamber 201;
The film containing Si, O, C, and N on the wafer 200, that is, a silicon oxycarbonitride film (SiOCN film), is performed a predetermined number of times (n times) by performing the cycle not performed simultaneously, that is, without synchronization. Form The SiOCN film can also be referred to as a silicon oxynitride film containing C (SiON film), a SiON film to which C is added (doped), or a C-containing SiON film.

When performing the above cycle a predetermined number of times,
Step 3p of discharging O ₂ gas and at least one of the gas discharging effect and efficiency in step 4p of discharging NH ₃ gas, Step 1 p of discharging HCDS gas and that in step 2p of discharging C ₃ H ₆ gas Or make them bigger than them.

  That is, the gas discharging effect in step 3p and the gas discharging effect in step 4p are respectively made larger than the gas discharging effect in step 1p and larger than the gas discharging effect in step 2p.

  Alternatively, the gas discharge efficiency in step 3p and the gas discharge efficiency in step 4p are respectively made larger than the gas discharge efficiency in step 1p and larger than the gas discharge efficiency in step 2p.

  Alternatively, the gas discharge effect in step 3p and the gas discharge effect in step 4p are respectively larger than the gas discharge effect in step 1p and larger than the gas discharge effect in step 2p, and the gas discharge efficiency in step 3p And the gas discharge efficiency in step 4p is made larger than the gas discharge efficiency in step 1p and larger than the gas discharge efficiency in step 2p, respectively.

  In the present specification, the above-described deposition sequence may be indicated as follows for convenience.

(HCDS → C ₃ H ₆ → O ₂ → NH ₃ ) × n SiO SiOCN

  When the word "wafer" is used in this specification, it means "wafer itself" or "laminate (aggregate) of a wafer and a predetermined layer or film formed on the surface". In the case of meaning, in other words, a predetermined layer or film formed on the surface may be referred to as a wafer. In addition, when the term "surface of wafer" is used in this specification, it means "surface (exposed surface) of wafer itself" or "surface of a predetermined layer or film or the like formed on a wafer" That is, it may mean "the outermost surface of the wafer as a laminate".

  Therefore, in the present specification, when "supplying a predetermined gas to a wafer" is described, it means "supplying a predetermined gas directly to the surface (exposed surface) of the wafer itself" or This may mean that "a predetermined gas is supplied to a layer, a film or the like formed on a wafer, that is, the outermost surface of a wafer as a laminate". Further, in the present specification, when "a predetermined layer (or film) is formed on a wafer" is described, "a predetermined layer (or film) is directly formed on the surface (exposed surface) of the wafer itself" Or “means to form a predetermined layer (or film) on a layer, film or the like formed on the wafer, ie, the outermost surface of the wafer as a laminate”. There is a case.

  In addition, when the word "substrate" is used in this specification, it is the same as the case where the word "wafer" is used. In that case, if "wafer" is replaced with "substrate" in the above description, it can be considered. Good.

(Wafer charge and boat load)
A plurality of wafers 200 are loaded into the boat 217 (wafer charging). Thereafter, as shown in FIG. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat loading). In this state, the seal cap 219 seals the lower end of the reaction tube 203 via the O-ring 220.

(Pressure adjustment and temperature adjustment)
The vacuum pump 246 evacuates (depressurizes and evacuates) the processing chamber 201, that is, the space in which the wafer 200 exists has a 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. The vacuum pump 246 maintains its operating state constantly at least until the processing on the wafer 200 is completed. Further, the wafer 200 in the processing chamber 201 is heated by the heater 207 so as to have a desired temperature. At this time, the degree of energization of the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. The heating of the inside of the processing chamber 201 by the heater 207 is continuously performed at least until the processing on the wafer 200 is completed. Also, the rotation of the boat 217 and the wafer 200 by the rotation mechanism 267 is started. The rotation of the boat 217 and the wafers 200 by the rotation mechanism 267 continues at least until the processing on the wafers 200 is completed.

(Process to form SiOCN film)
Thereafter, the following eight steps are sequentially executed: step 1, 1p, step 2, 2p, step 3, 3p, step 4, 4p.

[Step 1 (HCDS gas supply)]
In this step, the HCDS gas is supplied to the wafer 200 in the processing chamber 201.

The valve 243a is opened to flow the HCDS gas into the gas supply pipe 232a. The flow rate of the HCDS gas is adjusted by the MFC 241 a, supplied into the processing chamber 201 through the nozzle 249 a, and exhausted from the exhaust pipe 231. At this time, the HCDS gas is supplied to the wafer 200. At the same time, the valve 243c is opened to flow the N ₂ gas into the gas supply pipe 232c. The flow rate of the N ₂ gas is adjusted by the MFC 241 c, and the N ₂ gas is supplied into the processing chamber 201 together with the HCDS gas and exhausted from the exhaust pipe 231.

Further, in order to prevent the HCDS gas from intruding into the nozzle 249b, the valve 243d is opened to flow the N ₂ gas into the gas supply pipe 232d. The N ₂ gas is supplied into the processing chamber 201 through the gas supply pipe 232 b and the nozzle 249 b and exhausted from the exhaust pipe 231.

The supply flow rate of the HCDS gas controlled by the MFC 241 a is, for example, a flow rate within the range of 1 to 2000 sccm, preferably 10 to 1000 sccm. The supply flow rate of N ₂ gas controlled by the MFCs 241 c and 241 d is, for example, a flow rate within a range of 100 to 10000 sccm. The pressure in the processing chamber 201 is, for example, a pressure in the range of 1 to 2666 Pa, preferably 67 to 1333 Pa. The time for supplying the HCDS gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, a time within a range of 1 to 120 seconds, preferably 1 to 60 seconds. The temperature of the heater 207 is set such that the temperature of the wafer 200 is, for example, 250 to 700 ° C., preferably 300 to 650 ° C., more preferably 350 to 600 ° C.

  When the temperature of the wafer 200 is less than 250 ° C., the HCDS is less likely to be chemically adsorbed onto the wafer 200, and a practical deposition rate may not be obtained. By setting the temperature of the wafer 200 to 250 ° C. or more, it is possible to eliminate this. By setting the temperature of the wafer 200 to 300 ° C. or higher, and further to 350 ° C. or higher, HCDS can be more sufficiently adsorbed on the wafer 200, and a more sufficient film formation rate can be obtained.

  If the temperature of the wafer 200 exceeds 700 ° C., the CVD reaction becomes too strong (excess gas phase reaction occurs), the film thickness uniformity tends to deteriorate, and the control thereof becomes difficult. By setting the temperature of the wafer 200 to 700 ° C. or less, an appropriate gas phase reaction can be generated, so that the deterioration of the film thickness uniformity can be suppressed and the control thereof can be performed. In particular, by setting the temperature of the wafer 200 to 650 ° C. or less, and further to 600 ° C. or less, surface reaction becomes dominant over gas phase reaction, film thickness uniformity can be easily secured, and control thereof can be facilitated.

  Therefore, the temperature of the wafer 200 may be 250 to 700 ° C., preferably 300 to 650 ° C., and more preferably 350 to 600 ° C.

  By supplying the HCDS gas to the wafer 200 under the conditions described above, Si containing Cl containing Cl having a thickness of less than one atomic layer to several atomic layers, for example, as a first layer on the outermost surface of the wafer 200 A layer is formed. The Si-containing layer containing Cl may be a Si layer containing Cl, may be an adsorption layer of HCDS, or may include both of them.

  The Si layer containing Cl is a generic term including a continuous layer composed of Si and a continuous layer containing Cl, a discontinuous layer, and a Si thin film containing Cl formed by overlapping these layers. The continuous layer composed of Si and containing Cl may be referred to as a Si thin film containing Cl. Si constituting the Si layer containing Cl includes not only a completely broken bond with Cl but also a completely broken bond with Cl.

  The adsorption layer of HCDS includes a discontinuous adsorption layer as well as a continuous adsorption layer composed of HCDS molecules. That is, the adsorption layer of HCDS includes an adsorption layer having a thickness of one molecular layer or less than one molecular layer composed of HCDS molecules. The HCDS molecules constituting the adsorption layer of HCDS include those in which the bond between Si and Cl is partially broken. That is, the adsorption layer of HCDS may be a physical adsorption layer of HCDS, a chemical adsorption layer of HCDS, or both of them.

  Here, a layer having a thickness of less than 1 atomic layer means an atomic layer formed discontinuously, and a layer having a thickness of 1 atomic layer means an atomic layer formed continuously. Means. A layer having a thickness of less than one molecular layer means a molecular layer formed discontinuously, and a layer having a thickness of one molecular layer means a molecular layer formed continuously. ing. The Si-containing layer containing Cl may include both a Si layer containing Cl and an adsorption layer of HCDS. However, as described above, the Si-containing layer containing Cl is expressed using expressions such as “one atomic layer” and “several atomic layer”.

  Under the conditions under which the HCDS gas is self-decomposed (thermally decomposed), that is, under the conditions where the thermal decomposition reaction of the HCDS gas occurs, Si is deposited on the wafer 200 to form a Si layer containing Cl. Under the conditions in which the HCDS gas does not decompose (thermally decompose), that is, the conditions in which the thermal decomposition reaction of the HCDS gas does not occur, the HCDS is adsorbed on the wafer 200 to form an HCDS adsorption layer. Forming a Si layer containing Cl on the wafer 200 is preferable to forming an adsorption layer of HCDS on the wafer 200 in that the film forming rate can be increased.

  If the thickness of the first layer exceeds several atomic layers, the action of modification in steps 3 and 4 described later does not reach the entire first layer. In addition, the minimum value of the thickness of the first layer is less than one atomic layer. Therefore, the thickness of the first layer is preferably less than one atomic layer to several atomic layers. By setting the thickness of the first layer to one atomic layer or less, that is, less than one atomic layer or one atomic layer, the action of the modification reaction in steps 3 and 4 described later can be relatively enhanced. The time required for the reforming reaction in steps 3 and 4 can be shortened. The time required to form the first layer in step 1 can also be reduced. As a result, the processing time per cycle can be shortened, and the total processing time can also be shortened. That is, it is also possible to increase the deposition rate. In addition, by setting the thickness of the first layer to one atomic layer or less, controllability of film thickness uniformity can be enhanced.

As the source gas, in addition to HCDS gas, for example, OCTS gas, dichlorosilane (SiH ₂ Cl ₂ , abbreviation: DCS) gas, monochlorosilane (SiH ₃ Cl, abbreviation: MCS) gas, tetrachlorosilane, ie, silicon tetrachloride (SiCl 2) _4. An inorganic halosilane raw material gas such as an abbreviation: STC gas, trichlorosilane (SiHCl ₃ , abbreviation: TCS) gas, etc. can be used.

  In addition, as a source gas, an organic halosilane source gas such as BTCSE gas, BTCSM gas, TCDMDS gas, DCTMDS gas, MCPMDS gas and the like can be used.

In addition, as a source gas, for example, halogen group such as monosilane (SiH ₄ , abbreviation: MS) gas, disilane (Si ₂ H ₆ , abbreviation: DS) gas, trisilane (Si ₃ H ₈ , abbreviation: TS) gas etc. It is possible to use the contained inorganic silane source gas.

Moreover, as a source gas, for example, dimethylsilane (SiC ₂ H ₈ , abbreviation: DMS) gas, trimethylsilane (SiC ₃ H ₁₀ , abbreviation: TMS) gas, diethylsilane (SiC ₄ H ₁₂ , abbreviation: DES) gas It is also possible to use a halogen-group-free organic silane source gas such as 1,4-disilabutane (Si ₂ C ₂ H ₁₀ , abbreviated: DSB) gas.

As the raw material gas, for example, tris (dimethylamino) silane _{(Si [N (CH 3)} 2] 3 H, abbreviation: 3DMAS) Gas, tetrakis (dimethylamino) silane _{(Si [N (CH 3)} 2] 4, abbreviation: 4DMAS) Gas, bis-diethylaminosilane (Si [N (C ₂ H ₅ ) ₂ ] ₂ H ₂ , abbreviation: BDEAS) gas, Bister shary butylaminosilane (SiH ₂ [NH (C ₄ H ₉ )] ₂ , abbreviation: BTBAS) gas It is also possible to use a halogen group-free amino-based (amine-based) silane source gas such as, for example.

  When using an organic halosilane source gas or an organic silane source gas that also acts as a C source as a source gas, it becomes possible to include C in the first layer, and as a result, the final process on the wafer 200 is performed. It is possible to increase the C concentration in the SiOCN film which is formed as compared with the case where an inorganic halosilane source gas or an inorganic silane source gas is used as a source gas. In addition, when using an amino-based silane source gas that also acts as a C source and an N source as source gases, it becomes possible to include C and N in the first layer, and as a result, the final on the wafer 200 It becomes possible to respectively increase the C concentration and the N concentration in the SiOCN film formed as compared with the case of using an inorganic silane source gas as the source gas.

[Step 1p (HCDS gas discharge)]
After the first layer is formed, the valve 243a is closed to stop the supply of the HCDS gas. At this time, with the APC valve 244 kept open, the inside of the processing chamber 201 is evacuated by the vacuum pump 246 to process the HCDS gas after contributing to the formation of the unreacted or first layer remaining in the processing chamber 201. The chamber 201 is discharged. At this time, the valves 243 c and 243 d are kept open to maintain the supply of the N ₂ gas into the processing chamber 201. The N ₂ gas acts as a purge gas, whereby the effect of discharging the gas remaining in the processing chamber 201 from the processing chamber 201 can be enhanced.

At this time, the gas remaining in the processing chamber 201 may not be completely discharged, and the inside of the processing chamber 201 may not be completely purged. If the amount of gas remaining in the processing chamber 201 is small, no adverse effect occurs in step 2 performed thereafter. The flow rate of the N ₂ gas supplied into the processing chamber 201 does not have to be a large flow rate, for example, by supplying the N ₂ gas in an amount similar to the volume of the reaction tube 203 (processing chamber 201). The purge can be performed to such an extent that no adverse effect occurs. Thus, by not completely purging the inside of the processing chamber 201, the purge time can be shortened and the throughput can be improved. It is also possible to minimize the consumption of N ₂ gas.

As the inert gas, in addition to N ₂ gas, for example, rare gas such as Ar gas, He gas, Ne gas, Xe gas and the like can be used.

[Step 2 (C ₃ H ₆ gas supply)]
After step 1 p is completed, the thermally activated C ₃ H ₆ gas is supplied to the wafer 200 in the processing chamber 201, that is, the first layer formed on the wafer 200.

In this step, the open / close control of the valves 243a, 243c, 243d is performed in the same procedure as the open / close control of the valves 243a, 243c, 243d in step 1. The flow rate of the C ₃ H ₆ gas is adjusted by the MFC 241 a, supplied into the processing chamber 201 through the nozzle 249 a, and exhausted from the exhaust pipe 231. At this time, C ₃ H ₆ gas is supplied to the wafer 200.

The supply flow rate of the C ₃ H ₆ gas controlled by the MFC 241 a is, for example, a flow rate in the range of 100 to 10000 sccm. The pressure in the processing chamber 201 is, for example, a pressure in the range of 1 to 5000 Pa, preferably 1 to 4000 Pa. The partial pressure of the C ₃ H ₆ gas in the processing chamber 201 is, for example, a pressure in the range of 0.01 to 4950 Pa. By setting the pressure in the processing chamber 201 to such a relatively high pressure zone, it is possible to thermally activate the C ₃ H ₆ gas with non-plasma. When the C ₃ H ₆ gas is thermally activated and supplied, a relatively soft reaction can be generated, and formation of a C-containing layer described later is facilitated. The time for supplying C ₃ H ₆ gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, in the range of 1 to 200 seconds, preferably 1 to 120 seconds, and more preferably 1 to 60 seconds. It will be time. Other processing conditions are, for example, the same processing conditions as in step 1.

At this time, the gas flowing into the processing chamber 201 is a thermally activated C ₃ H ₆ gas, and no HCDS gas flows into the processing chamber 201. Therefore, the C ₃ H ₆ gas does not cause a gas phase reaction, and is supplied to the wafer 200 in an activated state. As a result, the carbon-containing layer (C-containing layer) is formed on the surface of the first layer formed on the wafer 200 in step 1, ie, the Si-containing layer containing Cl. The C-containing layer may be a C layer, an adsorption layer of C ₃ H ₆ , or both of them. The C-containing layer is a layer having a thickness of less than one molecular layer or less than one atomic layer, that is, a discontinuous layer. As a result, a second layer containing Si, Cl and C is formed on the outermost surface of the wafer 200. The second layer is a layer including a Cl-containing Si-containing layer and a C-containing layer. Depending on the conditions, a part of the first layer may react with the C ₃ H ₆ gas to reform (carbonize) the first layer, and the second layer may include the SiC layer. .

  The C-containing layer needs to be a discontinuous layer. When the C-containing layer is a continuous layer, the surface of the Si-containing layer containing Cl is entirely covered by the C-containing layer. In this case, Si does not exist on the surface of the second layer, and as a result, the oxidation reaction of the second layer in step 3 described later and the nitridation reaction of the third layer in step 4 described later are difficult. Can be Under the processing conditions as described above, O and N bond with Si but do not bond easily with C. In order to cause the desired reaction in Step 3 and Step 4 described later, the adsorption state of the C-containing layer on the Si-containing layer containing Cl was made unsaturated, and Si was exposed on the surface of the second layer It is necessary to be in the state. In addition, it becomes possible to make a C containing layer into a discontinuous layer by making the process conditions in step 2 into a process condition in the above-mentioned process condition range.

As the C-containing gas, in addition to C ₃ H ₆ gas, hydrocarbon-based gas such as acetylene (C ₂ H ₂ ) gas or ethylene (C ₂ H ₄ ) gas can be used.

[Step 2p (C ₃ H ₆ gas discharge)]
After the second layer is formed, the valve 243a is closed to stop the supply of C ₃ H ₆ gas. Then, C ₃ H ₆ gas and reaction byproducts after contributing to the formation of an unreacted or C-containing layer remaining in the processing chamber 201 from the inside of the processing chamber 201 by the same processing procedure and processing conditions as in step 1 p. Discharge. At this time, it is not necessary to completely discharge the gas and the like remaining in the processing chamber 201, as in step 1p. As the inert gas, in addition to the N ₂ gas, for example, various rare gases exemplified in Step 1 can be used.

[Step 3 (O ₂ gas supply)]
After step 2 p is completed, thermally activated O ₂ gas is supplied to the wafer 200 in the processing chamber 201, that is, the second layer formed on the wafer 200.

In this step, the opening and closing control of the valves 243b to 243d is performed in the same procedure as the opening and closing control of the valves 243a, 243c, and 243d in step 1. The flow rate of the O ₂ gas is adjusted by the MFC 241 b, supplied into the processing chamber 201 through the nozzle 249 b, and exhausted from the exhaust pipe 231. At this time, O ₂ gas is supplied to the wafer 200.

The supply flow rate of the O ₂ gas controlled by the MFC 241 b is, for example, a flow rate in the range of 100 to 10000 sccm. The pressure in the processing chamber 201 is, for example, a pressure in the range of 1 to 4000 Pa, preferably 1 to 3000 Pa. The partial pressure of O ₂ gas in the processing chamber 201 is, for example, a pressure in the range of 0.01 to 3960 Pa. By setting the pressure in the processing chamber 201 to such a relatively high pressure zone, it becomes possible to thermally activate the O ₂ gas with non-plasma. When the O ₂ gas is thermally activated and supplied, a relatively soft reaction can be generated, and the oxidation described later can be softened. The time for supplying the O ₂ gas to the wafer 200, that is, the gas supply time (irradiation time) is, eg, 1 to 120 seconds, preferably 1 to 60 seconds. Other processing conditions are, for example, the same processing conditions as in step 1.

At this time, the gas flowing into the processing chamber 201 is thermally activated O ₂ gas, and neither HCDS gas nor C ₃ H ₆ gas flows into the processing chamber 201. Therefore, the O ₂ gas does not cause a gas phase reaction, and is supplied to the wafer 200 in an activated state. The O ₂ gas supplied to wafer 200 includes the second layer (Si-containing layer containing Cl and C-containing layer) containing Si, Cl and C formed on wafer 200 in step 2 React with at least part of the layer). As a result, the second layer is thermally oxidized in a non-plasma manner to be transformed (reformed) into a third layer containing Si, O and C, ie, a silicon oxycarbonized layer (SiOC layer). ). When forming the third layer, the impurities such as Cl contained in the second layer constitute a gaseous substance containing at least Cl in the process of the reforming reaction with O ₂ gas, and the processing chamber It is discharged from the inside of 201. That is, an impurity such as Cl in the second layer is separated from the second layer by being extracted or separated from the second layer. Thus, the third layer is a layer having fewer impurities such as Cl and the like than the second layer.

  At this time, the oxidation reaction of the second layer is not saturated. For example, when a Si-containing layer containing Cl having a thickness of several atomic layers is formed in step 1 and a C-containing layer having a thickness of less than 1 atomic layer is formed in step 2, the surface layer Oxidize at least part of the layer). In this case, oxidation is performed under conditions where the oxidation reaction of the second layer is unsaturated so that the entire second layer is not oxidized. Depending on the conditions, it is possible to oxidize several layers below the surface layer of the second layer, but if only the surface layer is oxidized, the composition ratio of the SiOCN film finally formed on the wafer 200 Controllability can be improved, which is preferable. Also, for example, when a Si-containing layer containing Cl at a thickness of less than one atomic layer or less is formed in Step 1 and a C-containing layer having a thickness less than one atomic layer is formed in Step 2, for example, A portion of the surface layer is oxidized. Also in this case, the oxidation is performed under conditions where the oxidation reaction of the second layer is unsaturated so as not to oxidize the entire second layer. Note that, by setting the processing condition in step 3 as the processing condition within the above-described processing condition range, it is possible to make the oxidation reaction of the second layer unsaturated.

At this time, in particular, (or decrease the concentration) enhanced or a dilution ratio of O ₂ gas, or to shorten the supply time of the O ₂ gas, the processing conditions described above so as to lowering the partial pressure of O ₂ gas May be adjusted. For example, the dilution ratio of the reaction gas may be increased, the supply time of the reaction gas may be shortened, or the partial pressure of the reaction gas may be reduced, as compared with Steps 2 and 4. Thereby, the oxidizing power in step 3 can be appropriately reduced, and it becomes easier to make the oxidation reaction of the second layer unsaturated.

  By reducing the oxidizing power in step 3, it is possible to suppress the desorption of C from the second layer in the process of oxidation. Since the Si-O bond has a larger bond energy than the Si-C bond, forming the Si-O bond tends to break the Si-C bond. On the other hand, by appropriately reducing the oxidizing power in step 3, it is possible to suppress the breakage of the Si-C bond when forming the Si-O bond in the second layer, Si It is possible to suppress C from being released from the second layer.

  Further, by reducing the oxidizing power in step 3, it is possible to maintain the state in which Si is exposed on the outermost surface of the second layer after the oxidation treatment, that is, the third layer. By maintaining the state in which Si is exposed on the outermost surface of the third layer, it becomes easy to nitride the outermost surface of the third layer in Step 4 described later. When Si-O bonds and Si-C bonds are formed over the entire outermost surface of the third layer, and Si is not exposed on the outermost surface, Si-N bonds are not formed under the conditions of Step 4 described later It tends to be difficult to form. However, by maintaining the state in which Si is exposed on the outermost surface of the third layer, that is, Si that can be bonded to N under the conditions of Step 4 described later is present on the outermost surface of the third layer. By making it possible, it becomes easy to form a Si-N bond.

As the oxidizing gas, in addition to O ₂ gas, steam (H ₂ O gas), nitrogen monoxide (NO) gas, nitrous oxide (N ₂ O) gas, nitrogen dioxide (NO ₂ ) gas, carbon monoxide (CO) _2. ) O-containing gas such as gas, carbon dioxide (CO ₂ ) gas, ozone (O ₃ ) gas, etc. can be used.

[Step 3p (O ₂ gas discharge)]
After the third layer is formed, the valve 243 _b is closed to stop the supply of O ₂ gas. Then, the O ₂ gas and reaction byproducts after contributing to the formation of the unreacted or third layer remaining in the processing chamber 201 are discharged from the processing chamber 201. The processing procedure and processing conditions at this time will be described later. As the inert gas, in addition to the N ₂ gas, for example, various rare gases exemplified in Step 1 p can be used.

[Step 4 (NH ₃ gas supply)]
After step 3 p is completed, the thermally activated NH ₃ gas is supplied to the wafer 200 in the processing chamber 201, that is, the third layer formed on the wafer 200.

In this step, the opening and closing control of the valves 243b to 243d is performed in the same procedure as the opening and closing control of the valves 243a, 243c, and 243d in step 1. The flow rate of the NH ₃ gas is adjusted by the MFC 241 b, and is supplied into the processing chamber 201 through the nozzle 249 b and exhausted from the exhaust pipe 231. At this time, the NH ₃ gas is supplied to the wafer 200.

The supply flow rate of the NH ₃ gas controlled by the MFC 241 b is, for example, a flow rate in the range of 100 to 10000 sccm. The pressure in the processing chamber 201 is, for example, a pressure in the range of 1 to 4000 Pa, preferably 1 to 3000 Pa. The partial pressure of the NH ₃ gas in the processing chamber 201 is, for example, a pressure in the range of 0.01 to 3960 Pa. By setting the pressure in the processing chamber 201 to such a relatively high pressure zone, it is possible to thermally activate the NH ₃ gas with non-plasma. When the NH ₃ gas is thermally activated and supplied, a relatively soft reaction can be generated, and the below-described nitriding can be performed softly. The time for supplying the NH ₃ gas to the wafer 200, that is, the gas supply time (irradiation time) is, eg, 1 to 120 seconds, preferably 1 to 60 seconds. Other processing conditions are, for example, the same processing conditions as in step 1.

At this time, the gas flowing into the processing chamber 201 is thermally activated NH ₃ gas, and neither HCDS gas nor C ₃ H ₆ gas nor O ₂ gas flows into the processing chamber 201. Therefore, the NH ₃ gas does not cause a gas phase reaction, and is supplied to the wafer 200 in an activated state. The NH ₃ gas supplied to the wafer 200 reacts with at least a part of the third layer (SiOC layer) formed on the wafer 200 in step 3. As a result, the third layer is thermally nitrided non-plasma to be transformed into a fourth layer containing Si, O, C and N, ie, a silicon oxycarbonitriding layer (SiOCN layer) Quality). When forming the fourth layer, the impurities such as Cl contained in the third layer constitute a gaseous substance containing at least Cl in the process of the reforming reaction with NH ₃ gas, and the processing chamber It is discharged from the inside of 201. That is, the impurity such as Cl in the third layer is separated from the third layer by being extracted or separated from the third layer. As a result, the fourth layer becomes a layer having fewer impurities such as Cl and the like than the third layer.

Further, by supplying the activated NH ₃ gas to the wafer 200, the outermost surface of the third layer is reformed in the process of nitriding the third layer. In the outermost surface of the third layer after the surface modification treatment in the process of nitriding, ie, the outermost surface of the fourth layer, HCDS is easily adsorbed in Step 1 performed in the next cycle, and Si is It becomes a surface state which is easy to deposit. That is, the NH ₃ gas used in step 4 also acts as an adsorption and deposition promoting gas that promotes adsorption and deposition of HCDS and Si on the outermost surface of the fourth layer (the outermost surface of the wafer 200). .

  At this time, the nitriding reaction of the third layer is not saturated. For example, when the third layer having a thickness of several atomic layers is formed in Steps 1 to 3, at least a part of the surface layer (one atomic layer on the surface) is nitrided. In this case, the nitriding is performed under conditions where the nitriding reaction of the third layer becomes unsaturated so as not to nitride the whole of the third layer. Although it is possible to nitride several layers below the surface layer of the third layer depending on the conditions, the composition ratio of the SiOCN film finally formed on the wafer 200 can be obtained by nitriding only the surface layer. Controllability can be improved, which is preferable. Also, for example, when the third layer having a thickness of less than one atomic layer or less than one atomic layer is formed in Steps 1 to 3, a part of the surface layer is similarly nitrided. Also in this case, the nitriding is performed under conditions where the nitriding reaction of the third layer becomes unsaturated so as not to nitride the whole of the third layer. The nitriding reaction of the third layer can be made unsaturated by setting the processing condition in step 4 as the processing condition within the above-mentioned processing condition range.

As the nitriding gas, in addition to NH ₃ gas, hydrogen nitride-based gas such as diazene (N ₂ H ₂ ) gas, hydrazine (N ₂ H ₄ ) gas, N ₃ H ₈ gas, gas containing these compounds, etc. It can be used.

[Step 4p (NH ₃ gas discharge)]
After the fourth layer is formed, the valve 243 b is closed to stop the supply of NH ₃ gas. Then, the NH ₃ gas and reaction byproducts after contributing to the formation of the unreacted or fourth layer remaining in the processing chamber 201 are discharged from the processing chamber 201. The processing procedure and processing conditions at this time will be described later. As the inert gas, in addition to the N ₂ gas, for example, various rare gases exemplified in Step 1 p can be used.

(Performed number of times)
A SiOCN film of a predetermined composition and a predetermined film thickness can be formed on the wafer 200 by performing a predetermined number of times (n times) of the above-described eight steps non-simultaneously, that is, without synchronization. The above cycle is preferably repeated a plurality of times. That is, it is formed by making the thickness of the fourth layer (SiOCN layer) formed in one cycle of the above cycle smaller than the desired film thickness and laminating the fourth layer (SiOCN layer). It is preferable to repeat the above-described cycle a plurality of times until the film thickness of the SiOCN film reaches a desired film thickness.

(Purge and return to atmospheric pressure)
After the formation of the SiOCN film is completed, the valves 243 c and 243 d are opened to supply N ₂ gas from the gas supply pipes 232 c and 232 d into the processing chamber 201 and exhaust the gas from the exhaust pipe 231. The N ₂ gas acts as a purge gas. As a result, the inside of the processing chamber 201 is purged, and gas and reaction byproducts remaining in the processing chamber 201 are removed from the inside of the processing chamber 201 (purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas substitution), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure recovery).

(Boat unloading and wafer discharging)
The seal cap 219 is lowered by the boat elevator 115, and the lower end of the reaction tube 203 is opened. Then, the processed wafer 200 is carried out of the lower end of the reaction tube 203 to the outside of the reaction tube 203 while being supported by the boat 217 (boat unloading). The processed wafers 200 are taken out of the boat 217 (wafer discharge).

(3) Discharge step of O ₂ gas and NH ₃ gas In the above-described film forming sequence, steps 1 to 4 are performed not simultaneously. That is, after the residual gas and the like in the processing chamber 201 are removed by performing the steps 1p to 4p, the source gas (HCDS gas) and the reaction gas (O ₂ gas, NH ₃ gas, etc.) are supplied into the processing chamber 201 It is like that. Thus, the gas phase reaction between the source gas and the reaction gas in the processing chamber 201, for example, the gas phase reaction between the HCDS gas and the O ₂ gas, the gas phase reaction between the HCDS gas and the NH ₃ gas, etc. Is possible. As a result, generation of particles in the processing chamber 201 can be suppressed.

In the above-described film forming sequence, in Steps 3 and 4, the O ₂ gas and the NH ₃ gas are supplied through the nozzle 249 b different from the nozzle 249 a supplying the HCDS gas. Further, in step 1, the entry of the HCDS gas into the nozzle 249b is prevented by supplying the N ₂ gas into the nozzle 249b. In Steps 3 and 4, the N ₂ gas is supplied into the nozzle 249a to prevent the infiltration of the O ₂ gas or the NH ₃ gas into the nozzle 249a. As a result, it is possible to avoid the gas phase reaction between the HCDS gas and the O ₂ gas in the nozzles 249 a and 249 b and the gas phase reaction between the HCDS gas and the NH ₃ gas. As a result, generation of particles in the nozzles 249a and 249b can be suppressed.

However, according to the intensive researches of the inventors, the step 3p of discharging the O ₂ gas, the processing condition and the like in the step 4p of discharging the NH ₃ gas in the above film forming sequence are the steps 1p of discharging the HCDS gas, It was found that the amount of particles in the processing chamber 201 may increase if the processing conditions and the like in Step 2p of discharging the C ₃ H ₆ gas are the same. Specifically, when the processing procedure and processing conditions in steps 3p and 4p are the same as the processing procedure and processing conditions in steps 1p and 2p, when steps 3 and 4 are performed, a large amount of particles are generated in the nozzle 249b. It has been found that this may cause an increase in the amount of particles in the processing chamber 201, particularly in the vicinity of the nozzle 249b.

According to the inventors' earnest research, the above-mentioned phenomenon is a small amount of impurities contained in the inner surface (surface of the inner wall) of the nozzle 249b in the process of manufacturing the nozzle 249b, for example, iron (Fe) , titanium (Ti), to impurities including metal elements such as aluminum (Al), it was found that caused by being supplied in a state where O ₂ gas and NH ₃ gas are mixed. The particle generation mechanism is described in detail below.

After performing step 3 of supplying the O ₂ gas into the processing chamber 201 through the nozzle 249 b, performing step 3 p of discharging the O ₂ gas from the inside of the processing chamber 201, the nozzle 249 b is not only in the processing chamber 201 O ₂ gas is also discharged from the inside. However, depending on the processing procedure of step 3p and the processing conditions, a small amount of O ₂ gas may be adhered and remain in the nozzle 249b. The O ₂ gas remaining in the nozzle 249 b is mixed with the NH ₃ gas supplied into the nozzle 249 b in step 4 performed immediately after step 3 p. When the O ₂ gas and the NH ₃ gas are mixed in the nozzle 249 b, reaction of these gases may generate active radicals and the like including OH groups and the like. A large number of fine particles may be generated by the reaction of the radical with the impurity containing the metal element contained in the inner wall surface of the nozzle 249b.

In addition, after performing Step 4 of supplying NH ₃ gas into the processing chamber 201 via the nozzle 249 b, if Step 4 p of discharging NH ₃ gas from the inside of the processing chamber 201 is performed, not only in the processing chamber 201 but The NH ₃ gas is also discharged from the inside of the nozzle 249 b. However, as in the case of step 3p, depending on the process procedure and process conditions of step 4p, a small amount of NH ₃ gas may be adhered and remain in the nozzle 249b. The NH ₃ gas remaining in the nozzle 249 b will be mixed with the O ₂ gas supplied into the nozzle 249 b in step 3 in the next cycle. When the NH ₃ gas and the O ₂ gas are mixed in the nozzle 249 b, as in the above, these gases react with each other to generate active radicals and the like including an OH group. A large number of fine particles may be generated by the reaction of the radical with the impurity containing the metal element contained in the inner wall surface of the nozzle 249b.

  Therefore, in the film forming sequence in the present embodiment, at least one of the gas discharging effect and the efficiency in Step 3p and Step 4p is set to Step 1p in order to suppress generation of particles resulting from the above-mentioned reaction occurring in the nozzle 249b. And at or in step 2p.

For example, in the film forming sequence shown in FIG. 4, the gas discharging time (PT ₃ and PT _{4 in the} figure) in step ₃ p for discharging O ₂ gas and step 4 p for discharging NH ₃ gas is a step for discharging HCDS gas. The gas discharge times (PT ₁ and PT _{2 in the} figure) in step 2p of discharging 1p and C ₃ H ₆ gas are respectively made longer. That is, PT ₃ > PT ₁ and PT ₂ , and PT ₄ > PT ₁ and PT ₂ . By setting the processing conditions of steps 3p and 4p, that is, the gas discharge time in this way, the gas discharge effect in step 3p and the gas discharge effect in step 4p are respectively made greater than the gas discharge effect in step 1p, And, it becomes possible to make it larger than the gas discharge effect in step 2p.

Further, for example, in the film forming sequence shown in FIG. 5, the flow rate of N ₂ gas supplied into the processing chamber 201 in step 3p for discharging O ₂ gas and step 4p for discharging NH ₃ gas (PF ₃ , More than the supply flow rate of N ₂ gas (PF ₁ and PF _{2 in the} figure) supplying PF ₄ ) into the processing chamber 201 in step 1p of discharging HCDS gas and step 2p of discharging C ₃ H ₆ gas I try to make each larger. That is, PF ₃ > PF ₁ and PF ₂ , and PF ₄ > PF ₁ and PF ₂ . By thus setting the process conditions of steps 3p and 4p, that is, the supply flow rate of N ₂ gas acting as a purge gas, the gas discharge efficiency in step 3p and the gas discharge efficiency in step 4p are respectively the gas in step 1p. It is possible to make it larger than the discharge efficiency and larger than the gas discharge efficiency in step 2p. As a result, it is possible to make the gas discharging effect in step 3p and the gas discharging effect in step 4p larger than the gas discharging effect in step 1p and larger than the gas discharging effect in step 2p, respectively.

Further, for example, in the film forming sequence shown in FIG. 6, the inside of the processing chamber 201 is exhausted without supplying the gas into the processing chamber 201 (vacuum (vacuum) in step ₃ p for discharging O ₂ gas and step 4 p for discharging NH ₃ gas. Exhaust treatment (denoted by VAC in the figure) for exhausting, depressurizing evacuation, or evacuating, and purge treatment (PRG in the figure) for evacuating the inside of the processing chamber 201 while supplying N ₂ gas into the processing chamber 201 And (not shown) are performed non-simultaneously one by one, that is, alternately once. In the step 1p of discharging the HCDS gas and the step 2p of discharging the C ₃ H ₆ gas, respectively, the above-mentioned exhaust process (VAC) is not performed, and the process chamber 201 is supplied with the N ₂ gas into the process chamber 201. Only the purge process (PRG) for exhausting the inside is performed. By setting the processing procedures of steps 3p and 4p in this manner, the gas discharge efficiency in step 3p and the gas discharge efficiency in step 4p are respectively made larger than the gas discharge efficiency in step 1p, and the gas in step 2p It becomes possible to make it larger than the discharge efficiency. This is because when the exhaust process (VAC) and the purge process (PRG) are alternately performed, a pressure change occurs in the nozzle 249b and the like, and the pressure change remains due to adhesion to the inner surface of the nozzle 249b and the like. It is thought that this is due to the promotion of the discharge of reactive gases. As a result, it is possible to make the gas discharging effect in step 3p and the gas discharging effect in step 4p larger than the gas discharging effect in step 1p and larger than the gas discharging effect in step 2p, respectively.

Further, for example, in the film forming sequence shown in FIG. 7, the inside of the processing chamber 201 is exhausted without supplying the gas into the processing chamber 201 in step ₃ p for discharging O ₂ gas and step 4 p for discharging NH ₃ gas (vacuum A plurality of non-simultaneously, an exhaust process (VAC) to evacuate, depressurize or evacuate, and purge process (PRG) for exhausting the inside of the processing chamber 201 while supplying N ₂ gas into the processing chamber 201. That is, the cycle purge process which is alternately repeated a plurality of times is performed. FIG. 7 shows an example in which the number of repetitions of the cycle purge process performed in steps 3p and 4p is two. In the step 1p of discharging the HCDS gas and the step 2p of discharging the C ₃ H ₆ gas, respectively, the above-mentioned exhaust process (VAC) is not performed, and the process chamber 201 is supplied with the N ₂ gas into the process chamber 201. Only the purge process (PRG) for exhausting the inside is performed. By setting the processing procedures of steps 3p and 4p in this manner, the gas discharge efficiency in step 3p and the gas discharge efficiency in step 4p are respectively made larger than the gas discharge efficiency in step 1p, and the gas in step 2p It becomes possible to make it larger than the discharge efficiency. This is because when the exhaust process and the purge process are alternately repeated, pressure changes repeatedly occur in the nozzle 249b and the like, and the pressure change is discharged to the inner surface of the nozzle 249b and the like. Is thought to be by promoting As a result, it is possible to make the gas discharging effect in step 3p and the gas discharging effect in step 4p larger than the gas discharging effect in step 1p and larger than the gas discharging effect in step 2p, respectively.

When the gas discharge time (PT ₃ , PT ₄ ) in the steps 3p and 4p is the same length, the purge time (indicated as T _{1 in} FIG. 4) in the nozzle 249b between the steps 3 and 4 is the step 4, is shorter than the purge time in the nozzle 249 b (FIG. 4 shows the _{T 2)} between 3. That is, after the supply of O ₂ gas into the processing chamber 201 is stopped, the time T ₁ until the supply of NH ₃ gas into the processing chamber 201 is started is the supply of NH ₃ gas into the processing chamber 201. The time T ₂ until the start of the supply of O ₂ gas into the processing chamber 201 is shorter (T ₁ <T ₂ ). Therefore, the amount R4 of the reaction gas (O ₂ gas) remaining in the nozzle 249b immediately before the start of step ₄ is the reaction gas (NH 3) remaining in the nozzle 249b immediately before the start of step 3. ₃ ) the amount of gas (R ₄ > R ₃ ) tends to be larger than the amount R ₃ . The inventors set the amount of particles generated in the nozzle 249 b in step 4 (D ₄ ) in step 3 when the processing procedure and conditions in step 3 p are the same as the processing procedure and conditions in step 4 p. It was confirmed that the amount (D ₄ > D ₃ ) might be larger than the amount of particles (D ₃ ) generated in the nozzle 249b.

  Therefore, in order to reliably suppress the generation of particles in the nozzle 249b, it is preferable to make at least one of the gas discharging effect and the efficiency in step 3p larger than that in step 4p.

For example, in the film forming sequence shown in Figure 4, the gas discharge time PT ₃ in step 3p discharging the _{O 2} gas is preferably longer than the gas discharge time PT ₄ in step 4p for discharging NH ₃ gas. For example, if the gas supply times PT ₁ and PT ₂ in steps 1 p and 2 p are each 10 seconds, the gas discharge time PT ₃ in step 3 p may be 60 seconds and the gas discharge time PT ₄ in step 4 p may be 50 seconds. . Further, for example, in this case, the gas discharge time PT ₃ in step 3p and 50 seconds, the gas discharge time PT ₄ in step 4p may be 40 seconds. Further, for example, in this case, the gas discharge time PT ₃ in step 3p was 40 seconds, the gas discharge time PT ₄ in step 4p may be 30 seconds. By setting the processing conditions of steps 3p and 4p in this manner, it is possible to make the gas discharge effect in step 3p larger than the gas discharge effect in step 4p.

Further, for example, in the film forming sequence shown in FIG. 5, the supply flow rate PF ₃ of the N ₂ gas supplied into the processing chamber 201 in the step 3p of discharging the O ₂ gas is the processing chamber 201 in the step 4p of discharging the NH ₃ gas. It is preferable to make it larger than the supply flow rate PF ₄ of N ₂ gas supplied into the inside. For example, when the supply flow rates PF ₁ and PF ₂ of N ₂ gas in steps 1 p and ₂ p are ₂ slm, the supply flow rate PF ₃ of N ₂ gas in step 3 p is ₂₀ slm, and the supply flow rate PF of N ₂ gas in step 4 p ₄ may be 15 slm. Further, for example, in this case, the supply flow rate PF ₃ of _{N 2} gas in step 3p and 15 slm, a supply flow rate PF ₄ of _{N 2} gas in step 4p may be 10 slm. Further, for example, in this case, the supply flow rate PF ₃ of _{N 2} gas in step 3p and 10 slm, a supply flow rate PF ₄ of _{N 2} gas in step 4p may be 8 slm. By setting the processing conditions of steps 3p and 4p in this manner, it is possible to make the gas discharge efficiency in step 3p larger than the gas discharge efficiency in step 4p. As a result, the gas discharge effect in step 3p can be made greater than the gas discharge effect in step 4p.

Further, for example, in the film formation sequence shown in FIG. 7, O ₂ the execution count m ₃ cycles purging process performed in step 3p for discharging gas, cycle purging process execution count m ₄ which performs in step 4p for discharging NH ₃ gas It is preferable to use more. For example, step 1p, when to perform only purge process (PRG) in the 2p, the execution count _{m 3} at step 3p and 2 times, the number of executions _{m 4} in step 4p may be once. Further, for example, the number of executions m ₃ in step 3 p may be three, and the number of executions m ₄ in step 4 p may be two. Also, for example, the number of executions m ₃ in step 3 p may be _four, and the number of executions m ₄ in step 4 p may be three. By setting the processing conditions of steps 3p and 4p, that is, the number of times of performing the cycle purge in this manner, it is possible to make the gas discharge efficiency in step 3p larger than the gas discharge efficiency in step 4p. As a result, the gas discharge effect in step 3p can be made greater than the gas discharge effect in step 4p.

  Note that the various methods shown in FIGS. 4 to 7, that is, the various methods for enhancing the gas discharge efficiency and the discharge effect in steps 3p and 4p, can be used individually or in combination. It is possible.

(4) Effects of the Present Embodiment According to the present embodiment, one or more effects described below can be obtained.

(A) Remaining of O ₂ gas or NH ₃ gas in the nozzle 249 b by increasing at least one of the gas discharging effect and the efficiency in Step 3 p and Step 4 p than that in Step 1 p and Step 2 p Can be suppressed. As a result, it is possible to suppress the reaction between the O ₂ gas and the NH ₃ gas in the nozzle 249 b, that is, the generation of radicals and the like in the nozzle 249 b. As a result, generation of particles in the nozzle 249 b can be suppressed, and the amount of particles in the processing chamber 201 can be reduced. As a result, it is possible to improve the film quality of the SiOCN film formed on the wafer 200.

(B) The generation of particles in the nozzle 249 b can be more reliably suppressed by making at least one of the gas discharge effect and the efficiency in step 3 p larger than that in step 4 p, and It is possible to further reduce the amount of particles. Then, the film quality of the SiOCN film formed on the wafer 200 can be further improved.

(C) In steps 3 and 4, the O ₂ gas and the NH ₃ gas are supplied through the nozzle 249 b different from the nozzle 249 a supplying the HCDS gas. In addition, in step 1, the penetration of the HCDS gas into the nozzle 249b is prevented. Further, in Steps 3 and 4, infiltration of O ₂ gas or NH ₃ gas into the nozzle 249a is prevented. As a result, unnecessary gas phase reactions in the nozzles 249a and 249b can be avoided, and generation of particles in the nozzles 249a and 249b can be suppressed.

(D) Steps 1 to 4 are performed not simultaneously, that is, without synchronously supplying the source gas and the various reaction gases. This enables these gases to properly contribute to the reaction under conditions where the gas phase reaction and the surface reaction appropriately occur. As a result, excessive gas phase reaction in the processing chamber 201 can be avoided, and generation of particles can be suppressed. Further, the step coverage and the film thickness controllability of the SiOCN film formed on the wafer 200 can be improved.

(E) The productivity reduction of the film forming process is reduced by applying the various methods described above for improving the discharge efficiency and the discharge effect of the reaction gas only in Steps 3p and 4p and not applying to Steps 1p and 2p. It is possible to suppress the increase in film formation cost or to suppress the increase in film formation cost.

For example, the gas discharge time (PT ₁ , PT ₂ ) in the steps 1p, 2p is the time required to discharge the O ₂ gas or the NH ₃ gas from the inside of the nozzle 249 b in the steps 3p, 4p (PT ₃ , If the time is extended to the same degree as PT ₄ ), the time required for one cycle (cycle time) may be long, which may lower the productivity of the film forming process. Even when the same processing procedure (cycle purge processing) as steps 3p and 4p of the film forming sequence shown in FIG. 6 and FIG. 7 is applied to steps 1p and 2p, the cycle time is increased, and the film formation processing is produced. It may reduce the sex. Further, the supply flow rate (PF ₁ , PF ₂ ) of N ₂ gas supplied into the processing chamber 201 in the steps 1 p and ₂ p is to discharge the O ₂ gas and the NH ₃ gas from the nozzle 249 b in the steps 3 p and 4 p. If the flow rate is increased to the same level as the required N ₂ gas supply flow rate (PF ₃ , PF ₄ ), the amount of N ₂ gas consumed per cycle increases, and the film formation cost increases. There are times when you

  On the other hand, in the film forming sequence of the present embodiment, the above-described various methods for improving the discharge efficiency and the discharge effect of the reaction gas are applied only in the steps 3p and 4p, thereby suppressing the decrease in productivity of the film forming process. In addition, it is possible to suppress an increase in film formation cost.

(F) In the film forming sequence shown in FIGS. 6 and 7, the N ₂ gas is introduced into the processing chamber 201 in at least one of the step 3p for discharging the O ₂ gas and the step 4p for discharging the NH ₃ gas. The execution time of the purge process (PRG) for exhausting the inside of the processing chamber 201 while supplying is shorter than the execution time of the exhaust processing (VAC) for exhausting the inside of the processing chamber 201 without supplying the gas into the processing chamber 201. May be For example, in steps 3p and 4p, the implementation time of the exhaust process (VAC) may be 60 seconds, and the implementation time of the purge process (PRG) may be 30 seconds. In addition, in steps 3p and 4p, the implementation time of the exhaust process (VAC) may be set to 30 seconds, and the implementation time of the purge process (PRG) may be set to 15 seconds. In this case, it is possible to shorten the time required for steps 3p and 4p while maintaining the discharge efficiency and the discharge effect of the reaction gas (O ₂ gas, NH ₃ gas) from the inside of the nozzle 249b. As a result, it is possible to shorten the cycle time and improve the productivity of the film formation process. In addition, the amount of N ₂ gas consumed per cycle can be reduced to reduce the film formation cost.

(G) The above-described effects are obtained when a gas other than HCDS gas is used as the source gas, when a gas other than C ₃ H ₆ gas is used as the C-containing gas, or a gas other than O ₂ gas is used as the O-containing gas Also in the case of using gas other than NH ₃ gas as H-containing gas, it can be obtained similarly.

(5) Modified Example The film forming sequence in the present embodiment is not limited to the mode shown in FIG. 4 to FIG. 7 and can be changed as in the modified example shown below.

(Modifications 1 to 7)
The SiOCN film may be formed on the wafer 200 according to each film forming sequence (Modifications 1 to 7 in order from the top) shown in FIG.

In the first modification, first, a surface treatment step of pretreating (reforming) the surface of the wafer 200 is performed by supplying an NH ₃ gas as the H-containing gas to the wafer 200. Thereafter, a film forming sequence similar to the film forming sequence illustrated in FIGS. 4 to 7 is performed to form the SiOCN film on the wafer 200 after the surface processing. After the surface treatment step is completed, the step of discharging the NH ₃ gas from the inside of the processing chamber 201 is performed. At this time, if the NH ₃ gas remains in the nozzle 249 b, particles may be generated in the nozzle 249 b in the subsequent step of supplying the O ₂ gas. Therefore, in the step of discharging the NH ₃ gas to be performed after completion of the surface treatment step, e.g., step 4p similar procedure of the film-forming sequence shown in FIGS. 4 to 7, the processing conditions, NH ₃ from the processing chamber 201 Exhaust the gas. That is, in the timing C shown in Modification 1, steps similar to the procedure for discharging the NH ₃ gas performed at the timing B, the processing conditions, to discharge the NH ₃ gas from the processing chamber 201. At the timing A shown in the first modification, the O ₂ gas is discharged from the processing chamber 201 according to the same processing procedure and processing conditions as step 3 p of the film forming sequence shown in FIGS. 4 to 7.

In Modifications 2 to 7, the order and number of times of supply of the HCDS gas, C ₃ H ₆ gas, O ₂ gas, and NH ₃ gas are different from the film formation sequence shown in Modification 1. Also in these modifications, when the NH ₃ gas or O ₂ gas remains in the nozzle 249 b after the NH ₃ gas or O ₂ gas supply, the nozzle 249 b is provided in the subsequent step of supplying O ₂ gas or NH ₃ gas. Particles may occur inside. Therefore, at the timings of A to C shown in the modified examples 2 to 7, the inside of the processing chamber 201 is performed according to the same processing procedure and processing conditions as the reactive gas discharging step performed at the timings of A to C shown in the modified example 1, respectively. Exhaust NH ₃ gas or O ₂ gas from. In the second to seventh modifications, the surface treatment step may not be performed.

  Also by these modifications, the same effect as the film forming sequence shown in FIGS. 4 to 7 can be obtained. In addition, HCDS is easily adsorbed on the outermost surface of the wafer 200 after the pretreatment, and Si is easily deposited, so that the film formation process can be efficiently performed. It is also possible to improve the step coverage and in-plane film thickness uniformity of the film formed on the wafer 200.

In the modified examples 1, 2 and 6, as in the film forming sequence illustrated in FIGS. 4 to 7, at least the step of supplying O ₂ gas, the step of discharging O ₂ gas, and NH ₃ gas The step of supplying and the step of discharging the NH ₃ gas are continuously performed in this order. That is, immediately after the step of discharging the O ₂ gas at the timing of A, the step of supplying the NH ₃ gas to the wafer 200 is performed. Therefore, in these modifications, the step of discharging the NH ₃ gas at the timing of B or at least one of the gas discharging effect and the efficiency in the step of discharging the O ₂ gas at the timing of A, or from them It is preferable to make the For example, the gas discharge time in the step of discharging the O ₂ gas, or longer than that in the step of discharging the NH ₃ gas, or, N ₂ gas supplied in the step of discharging the O ₂ gas into the processing chamber 201 the supply flow rate of, preferably larger than that in the step of discharging the NH ₃ gas. In addition, it is preferable that the number of cycle purges performed in the step of discharging the O ₂ gas be greater than the number of cycles purge performed in the step of discharging the NH ₃ gas.

In the _third and fourth modifications, at least a step of supplying NH ₃ gas, a step of discharging NH ₃ gas, a step of supplying O ₂ gas, and a step of discharging O ₂ gas in this order I try to do it continuously. That is, immediately after the step of discharging the NH ₃ gas performed at the timing of A, the step of supplying the O ₂ gas to the wafer 200 is performed. Therefore, in these modifications, the step of discharging the O ₂ gas performed at the timing of B or at least one of the gas discharging effect and the efficiency in the step of discharging the NH ₃ gas performed at the timing of A or It is preferable to make the For example, the gas discharge time in the step of discharging the NH ₃ gas is made longer than that in the step of discharging the O ₂ gas, or the N ₂ gas supplied into the processing chamber 201 in the step of discharging the NH ₃ gas the supply flow rate of, preferably larger than that in the step of discharging the O ₂ gas. In addition, it is preferable that the number of cycle purges performed in the step of discharging the NH ₃ gas be greater than the number of cycles purge performed in the step of discharging the O ₂ gas.

Further, in the modified examples 4 and 7, the step of supplying the HCDS gas or the C ₃ H ₆ gas is interposed between the step of supplying the NH ₃ gas and the step of supplying the O ₂ gas. Therefore, in these modifications, at least one of the gas discharging effect and the efficiency in the step of discharging the reaction gas performed at the timing of A is equivalent to that of the step of discharging the reaction gas performed at the timing of B or It is also good.

In the first to seventh modifications, after performing the surface processing step, the wafer 200 is supplied with O ₂ gas (or NH ₃ gas) first to the wafer 200 in the first cycle. The step of supplying HCDS gas and C ₃ H ₆ gas is performed. Therefore, in the first, second, _third , fifth, and sixth modifications, the reaction gas for discharging the NH ₃ gas at the timing of C at least one of the gas discharging effect and the efficiency at the timing of A is discharged at the timing of A. At least one of the gas discharge effect and the efficiency in the step of Further, in the modified examples 1, 2, ₃ and 5, the step of discharging the reaction gas at the timing of B at least one of the gas discharging effect and the efficiency in the step of discharging the NH ₃ gas performed at the timing of C. It may be equal to at least one of the gas discharge effect and the efficiency in Further, in the modified examples 4 and 7, the gas in the step of discharging the reaction gas in the timing of A or B, at least one of the gas discharging effect and the efficiency in the step of discharging the NH ₃ gas performed in the timing of C. It may be equal to at least one of the emission effect and the efficiency.

(Modifications 8 to 10)
A SiOCN film or a silicon oxycarbonized film (SiOC film) may be formed on the wafer 200 according to each film forming sequence (Modifications 8 to 10 in order from the top) shown in FIG. Also in these modifications, after the supply of the TEA gas or the O ₂ gas is stopped, if the TEA gas or the O ₂ gas remains in the nozzle 249 b, the step of supplying the O ₂ gas or the TEA gas is performed. , Particles may occur in the nozzle 249b. Therefore, at the timings of A and B shown in the modified examples 8 to 10, the TEA from the processing chamber 201 is performed according to the processing procedure and processing conditions similar to the steps 3p and 4p of the film forming sequence shown in FIGS. Evacuate gas or O ₂ gas. Also by these modifications, the same effect as the film forming sequence shown in FIGS. 4 to 7 can be obtained. Incidentally, in the modified example 8-10, to increase the oxidizing power of the O ₂ gas may be an O ₂ gas to be supplied by plasma excitation. In this case, it becomes easy to form an N-free SiOC film on the wafer 200.

In the eighth modification, at least one of the gas discharging effect and the efficiency in the step of discharging the TEA gas performed at the timing of A is larger than that at the step of discharging the O ₂ gas performed at the timing of B or It is preferable to do. Further, in the modified examples 9 and 10, the step of discharging the TEA gas performed at the timing of B, or at least one of the gas discharging effect and the efficiency in the step of discharging the O ₂ gas performed at the timing of A It is preferable to make the The reasons for these and the specific method for obtaining the desired exhaust effect and the like are as described in the film forming sequence shown in FIG.

(Modifications 11 to 13)
A silicon oxynitride film (SiON film) may be formed on the wafer 200 according to each film forming sequence (Modifications 11 to 13 in order from the top) shown in FIG. Also in these modifications, if the NH ₃ gas or the O ₂ gas remains in the nozzle 249 b after stopping the supply of the NH ₃ gas or the O ₂ gas, the O ₂ gas or the NH ₃ gas to be performed thereafter is used. In the supplying step, particles may be generated in the nozzle 249 b. Therefore, at the timings of A and B shown in the modified examples 11 to 13, the NH from the processing chamber 201 is performed according to the processing procedure and processing conditions similar to the steps 3p and 4p of the film forming sequence shown in FIGS. ₃ Evacuate gas or O ₂ gas. Also by these modifications, the same effect as the film forming sequence shown in FIGS. 4 to 7 can be obtained.

In the modification 11, at least one of the gas discharging effect and the efficiency in the step of discharging the NH ₃ gas performed at the timing of A is at least the other of the steps of discharging the O ₂ gas performed at the timing of B or It is preferable to make it large. Further, in the modified examples 12 and 13, the step of discharging the NH ₃ gas at the timing of B or at least one of the gas discharging effect and the efficiency in the step of discharging the O ₂ gas at the timing of A or It is preferable to make it larger. The reasons for these and the specific method for obtaining the desired exhaust effect and the like are as described in the film forming sequence shown in FIG.

(Modifications 14 to 16)
A silicon oxide film (SiO film) may be formed on the wafer 200 according to each film forming sequence (Modifications 14 to 16 in order from the top) shown in FIG. Also in these modifications, if the H ₂ gas or the O ₂ gas remains in the nozzle 249 b after stopping the supply of the H ₂ gas or the O ₂ gas, the O ₂ gas or the H ₂ gas to be performed thereafter is used. In the supplying step, particles may be generated in the nozzle 249 b. Therefore, at the timings of A and B shown in the modified examples 14 to 16, H from the inside of the processing chamber 201 according to the processing procedure and processing conditions similar to the steps 3p and 4p of the film forming sequence shown in FIGS. ₂ Exhaust the gas or O ₂ gas. Also by these modifications, the same effect as the film forming sequence shown in FIGS. 4 to 7 can be obtained. In modifications 14 to 16, H ₂ gas or O ₂ gas may be plasma-excited and supplied.

In the modification 14, at least one of the gas discharging effect and the efficiency in the step of discharging the H ₂ gas performed at the timing of A is more than that in the step of discharging the O ₂ gas performed at the timing of B or It is preferable to make it large. In the modified examples 15 and 16, the step of discharging the H ₂ gas at the timing of B or at least one of the gas discharging effect and the efficiency in the step of discharging the O ₂ gas at the timing of A, or It is preferable to make it larger. The reasons for these and the specific method for obtaining the desired exhaust effect and the like are as described in the film forming sequence shown in FIG.

(Processing condition)
In the above-described modification, in the step of supplying the thermally activated TEA gas to the wafer 200, the supply flow rate of the TEA gas controlled by the MFC 241b is, for example, a flow rate within the range of 100 to 10000 sccm. The pressure in the processing chamber 201 is, for example, a pressure in the range of 1 to 5000 Pa, preferably 1 to 4000 Pa. Further, the partial pressure of the TEA gas in the processing chamber 201 is, for example, a pressure in the range of 0.01 to 4950 Pa. The time for supplying the TEA gas to the wafer 200, that is, the gas supply time (irradiation time) is, for example, 1 to 200 seconds, preferably 1 to 120 seconds, and more preferably 1 to 60 seconds. . Other processing conditions are, for example, the same processing conditions as step 4 of the film forming sequence shown in FIGS. 4 to 7. As the gas containing N, C and H, other than TEA gas, for example, diethylamine ((C ₂ H ₅ ) ₂ NH, abbreviation: DEA) gas, monoethylamine (C ₂ H ₅ NH ₂ , abbreviation: MEA) gas Etc., trimethylamine ((CH ₃ ) ₃ N, abbreviation: TMA) gas, dimethylamine ((CH ₃ ) ₂ NH, abbreviation: DMA) gas, monomethylamine (CH ₃ NH ₂ , abbreviation: MMA) A methylamine-based gas such as a gas can be used.

  The processing procedure and processing conditions in the other steps can be, for example, similar to the processing procedure and processing conditions of each step in the film forming sequence illustrated in FIGS. 4 to 7.

Another Embodiment of the Present Invention
The embodiments of the present invention have been specifically described above. However, the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the scope of the invention.

  For example, in the above-mentioned embodiment, after supplying source gas, an example which supplies reaction gas (C containing gas, O containing gas, H containing gas) was explained. The present invention is not limited to such a form, and the supply order of the source gas and the reaction gas may be reversed. That is, as in the modified examples 2, 10, 13, 16 and so on, the source gas may be supplied after the reaction gas is supplied. By changing the supply order, it is possible to change the film quality and the composition ratio of the thin film to be formed. In addition, the supply order of a plurality of types of reaction gases can be arbitrarily changed. By changing the supply order of the reaction gas, it is possible to change the film quality and the composition ratio of the thin film to be formed. Also, it is possible to supply a plurality of types of reaction gases in any combination and simultaneously, that is, to mix and use any combination. This makes it possible to change the film quality and the composition ratio of the thin film to be formed.

Further, for example, in the above-described embodiment, an example in which the O-containing gas (O ₂ gas) and the H-containing gas (NH ₃ gas) are supplied into the processing chamber 201 through the same nozzle 249 b has been described. The present invention is not limited to such a form, and the O-containing gas and the H-containing gas may be supplied into the processing chamber 201 through separate nozzles. For example, a nozzle (hereinafter, also referred to as a third nozzle) different from the nozzles 249a and 249b is newly provided in the processing chamber 201, and O ₂ gas is supplied through the nozzle 249b in step 3, and NH ₃ gas in step 4 May be supplied through the third nozzle.

The O ₂ gas supplied into the processing chamber 201 in step 3 may slightly intrude into the third nozzle. In addition, the NH ₃ gas supplied into the process chamber 201 in step 4 may slightly intrude into the nozzle 249 b. In these cases, the O ₂ gas and the NH ₃ gas may react with each other in the third nozzle or the nozzle 249 b, and a large number of fine particles may be generated in the third nozzle or the nozzle 249 b. Inventors, in case of supplying the O ₂ gas and NH ₃ gas from separate nozzles also, step 3p, step processing conditions in 4p 1p, if the same as the like treatment conditions in 2p, the processing chamber 201 In particular, it has been confirmed that the amount of particles in the vicinity of the third nozzle and in the vicinity of the nozzle 249b may increase.

Therefore, even in the case of supplying O ₂ gas and NH ₃ gas from separate nozzles, at least one of the gas discharging effect and the efficiency in step 3 p and step 4 p as in the above embodiment, step 1 p and step 1 p Make it larger than that in step 2p. This makes it possible to suppress the generation of particles in the nozzle 249 b and in the third nozzle. That is, not only in the case where O ₂ gas and NH ₃ gas are supplied from the same nozzle, but also in the case where they are supplied from separate nozzles, the gas discharging effect and efficiency in steps 3p and 4p are set as described above. The O ₂ gas and the NH ₃ gas are prevented from being mixed (not mixed) in the same nozzle, that is, in the same space. This makes it possible to suppress the generation of particles in the nozzle. However, towards the aforementioned embodiments is supplied through the same nozzle and O ₂ gas and NH ₃ gas, than when supplying these gases through separate nozzles, O ₂ gas and NH ₃ gas There is a high probability of reaction in the nozzle, and particles are likely to be generated. Therefore, the technical significance of setting the gas discharge effect and efficiency in steps 3p and 4p as described above is more important than the case where O ₂ gas and NH ₃ gas are supplied through separate nozzles. Is larger in the case of feeding through the same nozzle.

Further, for example, in the embodiment described above, the O-containing gas (O ₂ gas) and H-containing gas (NH ₃ gas), the L-shaped provided at a side of the wafer arrangement region long nozzle (nozzle 249 b) An example of horizontally supplying from the side of the wafer arrangement area has been described. The present invention is not limited to such a form, and the O-containing gas and the H-containing gas are directed from the upper side to the lower side of the wafer arrangement region through the short nozzles provided above or below the wafer arrangement region. Alternatively, they may be supplied upward from below. That is, the nozzles for supplying the O-containing gas and the H-containing gas are not long nozzles provided on the side of the wafer array area, but are provided above or below the wafer array area and above or above the wafer array area. You may use the short nozzle which has a gas supply hole below.

Also in this case, if the processing conditions and the like in steps 3p and 4p are the same as the processing conditions and the like in steps 1p and 2p, the NH ₃ gas or O ₂ gas supplied into the processing chamber 201 starts steps 3 and 4. In some cases, the gas may not be sufficiently discharged during the process and may be adhered to the inside of the processing chamber 201 to remain. In this state, when steps 3 and 4 are started, the O ₂ gas and the NH ₃ gas react in the processing chamber 201, and the radicals and the like generated by this reaction form the inner surface of the reaction tube 203 (the inner wall of the processing chamber 201). Reacts with impurities containing metallic elements such as Fe, Ti, and Al, which are contained in a slight amount, may generate a large amount of fine particles. As in the case of the nozzle 249b, etc., a slight amount of the impurity containing the above-mentioned metal element is attached or mixed in the inner surface (surface of the inner wall) of the reaction tube 203 made of quartz etc. As a result, the inner surface of the reaction tube 203 contains the above-mentioned impurities. In addition, the above-mentioned radicals or the like may react with the upper surface of the seal cap 219 made of a metal such as SUS, and a large number of fine particles may be generated.

Therefore, even when O ₂ gas and NH ₃ gas are supplied through the short nozzle, as in the above embodiment, at least one of the gas discharging effect and the efficiency in step 3 p and step 4 p is set to step 1 p And make it larger than that in step 2p. This makes it possible to suppress the generation of particles in the processing chamber 201. That is, even when O ₂ gas and NH ₃ gas are supplied through the short nozzle, the gas discharge effect and efficiency in steps 3 p and 4 p are set as described above, and O ₂ gas and NH ₃ gas are used. Are not mixed in the processing chamber 201, that is, in the same space (not mixed). This makes it possible to suppress the generation of particles in the processing chamber 201. However, in the above-described embodiment in which the O ₂ gas and the NH ₃ gas are supplied through the long nozzle, the O ₂ gas and the NH ₃ gas are more than in the case where these gases are supplied through the short nozzle. The probability of reaction is high and particles are more likely to be generated. Therefore, the technical significance of setting the gas discharge effect and efficiency in steps 3p and 4p as described above is higher than the case of supplying O ₂ gas and NH ₃ gas via a short nozzle. The feed through the long nozzle is larger.

  By using a silicon-based insulating film formed by the film forming sequence shown in FIGS. 4 to 7 and the method of each modification as a sidewall spacer, a device forming technique with less leakage current and excellent processability is provided. It becomes possible. In addition, by using the above-described silicon-based insulating film as an etch stopper, it is possible to provide a device formation technique excellent in processability. Further, according to the film forming sequence shown in FIG. 4 to FIG. 7 and some of the modifications, it is possible to form a silicon-based insulating film having an ideal stoichiometric ratio without using plasma. Since a silicon-based insulating film can be formed without using plasma, it is also possible to apply to a process that is concerned with plasma damage, such as a DPT SADP film.

  The above-described deposition sequence is performed on the wafer 200 using titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), niobium (Nb), aluminum (Al), molybdenum (Mo), tungsten (W) And the like, i.e., when forming an oxide film containing a metal element such as a metal element), i.e., a metal-based oxide film, it is preferably applicable. That is, the above-described film forming sequence is performed on the wafer 200 using TiOCN film, TiOC film, TiON film, TiO film, ZrOCN film, ZrOC film, ZrON film, ZrO film, HfOCN film, HfOC film, HfON film, HfO film, TaOCN film, TaOC film, TaON film, TaO film, NbOCN film, NbOC film, NbON film, NbO film, NbO film, AlOCN film, AlOC film, AlON film, AlO film, AlO film, MoOCN film, MoOC film, MoON film, MoO film, WOCN film Also when forming a WOC film, a WON film, and a WO film, it is possible to apply suitably.

When forming a metal-based oxide film, for example, titanium tetrachloride (TiCl ₄ ) gas, titanium tetrafluoride (TiF ₄ ) gas, zirconium tetrachloride (ZrCl ₄ ) gas, and zirconium tetrafluoride (ZrF ₄ ) are used as source gases. ) Gas, hafnium tetrachloride (HfCl ₄ ) gas, hafnium tetrafluoride (HfF ₄ ) gas, tantalum pentachloride (TaCl ₅ ) gas, tantalum pentafluoride (TaF ₅ ) gas, niobium pentachloride (NbCl ₅ ) gas, niobium pentafluoride (NbF ₅₎ gas, aluminum trichloride (AlCl ₃₎ gas, aluminum trifluoride (AlF ₃₎ gas, molybdenum pentachloride (MoCl ₅₎ gas It can be used molybdenum pentafluoride (MoF ₅₎ Gas, tungsten hexachloride (WCl ₆₎ gas, a tungsten hexafluoride (WF ₆₎ inorganic metal source gas containing a metal element and a halogen element such as a gas. In addition, as a source gas, for example, an organic metal source gas containing a metal element such as trimethylaluminum (Al (CH ₃ ) ₃ , abbreviation: TMA) gas and carbon can also be used. As the reaction gas, the same gas as that of the above embodiment can be used.

For example, a TiON film or a TiO film can be formed on the wafer 200 by the film forming sequence (the film forming sequence examples 1 to 3 in order) shown in FIG. The processing procedure and processing conditions in each step of the film forming sequence can be, for example, the same processing procedure and processing conditions as those of the above-described embodiment. At timings A and B shown in FIG. 12, the NH ₃ gas or the inside of the processing chamber 201 is processed according to the processing procedure and processing conditions similar to steps 3p and 4p of the film forming sequence shown in FIGS. Exhaust O ₃ gas.

In the film formation sequence example 1, the step of discharging the O ₃ gas performed at the timing of B or at least one of the gas discharge effect and the efficiency in the step of discharging the NH ₃ gas performed at the timing of A or It is preferable to make it larger. Further, in the film forming sequence examples 2 and 3, the steps in the step of discharging the NH ₃ gas in the timing of B, at least one of the gas discharge effect and the efficiency in the step of discharging the O ₃ gas in the timing of A. Or it is preferable to make them larger than them. These reasons and the specific method for obtaining the desired exhaust effect etc. are as described in the above embodiment.

  That is, the present invention can be suitably applied when forming a film containing a predetermined element such as a semiconductor element or a metal element.

  The process recipe (a program that describes the processing procedure and processing conditions of the substrate processing) used to form these various thin films is the content of the substrate processing (type of film to be formed, composition ratio, film quality, film thickness, processing It is preferable to prepare each separately (plurally prepared) according to the procedure, processing conditions, etc.). Hereinafter, the process recipe is simply referred to as a recipe. Then, when starting the substrate processing, it is preferable to appropriately select an appropriate recipe from among a plurality of recipes according to the content of the substrate processing. Specifically, a storage device provided in the substrate processing apparatus via a telecommunication line and a recording medium (external storage device 123) storing the plurality of recipes individually prepared according to the contents of the substrate processing It is preferable to store (install) in advance in 121c. Then, when starting the substrate processing, it is preferable that the CPU 121a included in the substrate processing apparatus appropriately selects an appropriate recipe from among a plurality of recipes stored in the storage device 121c in accordance with the content of the substrate processing. . With this configuration, it is possible to form films of various film types, composition ratios, film qualities, and film thicknesses in a versatile manner and with high reproducibility by one substrate processing apparatus. In addition, it is possible to reduce the operation burden of the operator (input burden and the like of the processing procedure and the processing conditions), and to start the substrate processing quickly while avoiding the operation error.

  The process recipe described above is not limited to the case of creating a new one, and may be prepared, for example, by changing an existing recipe already installed in the substrate processing apparatus. When changing the recipe, the changed recipe may be installed in the substrate processing apparatus via the telecommunication line or the recording medium recording the recipe. Alternatively, the existing recipe that has already been installed in the substrate processing apparatus may be directly changed by operating the input / output device 122 provided in the existing substrate processing apparatus.

  In the above-mentioned embodiment, the example which forms a thin film using the batch type substrate processing apparatus which processes a plurality of substrates at once was explained. The present invention is not limited to the above-described embodiment, and can be suitably applied to, for example, the case where a film is formed using a sheet-fed substrate processing apparatus that processes one or several substrates at a time. Further, in the above-described embodiment, the example of forming the film using the substrate processing apparatus having the hot wall type processing furnace has been described. The present invention is not limited to the above-described embodiment, and can be suitably applied to the case of forming a film using a substrate processing apparatus having a cold wall type processing furnace. Also in these cases, the processing procedure and processing conditions can be, for example, the same processing procedure and processing conditions as those of the above-described embodiment.

  For example, even in the case of forming a film using a substrate processing apparatus provided with a processing furnace 302 shown in FIG. 16A, the present invention can be suitably applied. The processing furnace 302 has a processing container 303 forming the processing chamber 301, a shower head 303s as a gas supply unit for supplying a gas in a shower shape into the processing chamber 301, and one or several wafers 200 in a horizontal posture. A support base 317 to support, a rotating shaft 355 supporting the support base 317 from below, and a heater 307 provided on the support base 317 are provided. The inlet (gas inlet) of the shower head 303s is connected to a gas supply port 332a for supplying the above-described source gas and a gas supply port 332b for supplying the above-described reaction gas. A gas supply system similar to the source gas supply system of the above-described embodiment is connected to the gas supply port 332a. The gas supply system similar to the reaction gas supply system of the above-mentioned embodiment is connected to gas supply port 332b. At the outlet (gas outlet) of the shower head 303s, a gas dispersion plate for supplying a gas into the processing chamber 301 in a shower shape is provided. The shower head 303 s is provided at a position facing the surface of the wafer 200 loaded into the processing chamber 301. In the processing container 303, an exhaust port 331 for exhausting the inside of the processing chamber 301 is provided. An exhaust system similar to the exhaust system of the above-described embodiment is connected to the exhaust port 331.

  Further, for example, the present invention can be suitably applied also in the case of forming a film using a substrate processing apparatus provided with a processing furnace 402 shown in FIG. 16 (b). The processing furnace 402 includes a processing container 403 forming the processing chamber 401, a support 417 supporting the one or several wafers 200 in a horizontal posture, a rotary shaft 455 supporting the support 417 from below, a processing container A lamp heater 407 for emitting light toward the wafer 200 in the portion 403 and a quartz window 403 w for transmitting the light of the lamp heater 407 are provided. The processing vessel 403 is connected to a gas supply port 432a for supplying the above-described source gas and a gas supply port 432b as a gas supply unit for supplying the above-described reaction gas. The gas supply system similar to the source gas supply system of the above-mentioned embodiment is connected to the gas supply port 432a. A gas supply system similar to the reaction gas supply system of the above-described embodiment is connected to the gas supply port 432b. The gas supply ports 432 a and 432 b are provided on the side of the end of the wafer 200 loaded into the processing chamber 401, that is, at a position not facing the surface of the wafer 200 loaded into the processing chamber 401. The processing container 403 is provided with an exhaust port 431 for exhausting the inside of the processing chamber 401. An exhaust system similar to the exhaust system of the above-described embodiment is connected to the exhaust port 431.

  In the case of using these substrate processing apparatuses, film formation can be performed under the same sequence and processing conditions as those of the above-described embodiment and modification, and the same effects as those of the above-described embodiment and modification can be obtained.

  Moreover, the above-mentioned embodiment, modification, etc. can be used combining suitably. Further, the processing conditions at this time can be, for example, the same processing conditions as those of the above-described embodiment.

  Hereinafter, the experimental result which supports the effect obtained by the above-mentioned embodiment and modification is explained.

As the sample 1, SiOCN films were formed on a plurality of wafers by the film forming sequence shown in FIG. 6 using the substrate processing apparatus in the above-described embodiment. A HCDS gas was used as a source gas, a C ₃ H ₆ gas as a C-containing gas, an O ₂ gas as an O-containing gas, and an NH ₃ gas as an H-containing gas. In the steps of discharging the O ₂ gas and discharging the NH ₃ gas, the execution time of the exhaust treatment (VAC) and the execution time of the purge treatment (PRG) were both set to 30 seconds, respectively. The other processing conditions were the conditions within the processing condition range described in the above embodiment.

As the sample 2, SiOCN films were formed on a plurality of wafers according to the film forming sequence shown in FIG. 6 using the substrate processing apparatus in the above-described embodiment. In the steps of discharging the O ₂ gas and discharging the NH ₃ gas, the execution time of the exhaust treatment (VAC) and the execution time of the purge treatment (PRG) were respectively 15 seconds. Other processing conditions were the same as in the case of preparing sample 1.

As the sample 3, SiOCN films were formed on a plurality of wafers according to the film forming sequence shown in FIG. 7 using the substrate processing apparatus in the above-described embodiment. In the steps of discharging the O ₂ gas and discharging the NH ₃ gas, the execution time of the exhaust treatment (VAC) and the execution time of the purge treatment (PRG) were respectively 15 seconds. The number of executions (m ₃ ) of cycle purge processing performed in the step of discharging O ₂ gas and the number of executions (m ₄ ) of cycle purge processing performed in the step of discharging NH ₃ gas were each two. Other processing conditions were the same as in the case of preparing sample 1.

As a sample 4, using the substrate processing apparatus of the above-described embodiment, the step of supplying the HCDS gas to the processing chamber of the wafer, a step of discharging the HCDS gas from the processing chamber, C ₃ to the processing chamber of the wafer and supplying the H ₆ gas, a step for discharging the C ₃ H ₆ gas from the processing chamber, and supplying O ₂ gas to the processing chamber of the wafer, a step of discharging the O ₂ gas from the processing chamber The step of supplying the NH ₃ gas to the wafers in the processing chamber, and the step of discharging the NH ₃ gas from the processing chamber in a non-simultaneous order in this order are performed a predetermined number of times to perform SiOCN on a plurality of wafers. A film was formed. The processing conditions and procedures of each step of discharging HCDS gas, C ₃ H ₆ gas, O ₂ gas, and NH ₃ gas from the processing chamber were common. Specifically, in each of these steps, only the purge process (PRG) is performed, and the execution time is 6 seconds. Other processing conditions were the same as in the case of preparing sample 1.

Then, the number of particles in the wafer of Samples 1 to 4 was measured in each of the upper, central, and lower portions in the wafer arrangement region, and the average value thereof was calculated. As a result, in the wafers of Samples 1 to 4, the average values described above were 11, 21, 15, and 94, respectively. Comparing the above average values of samples 1 to 3 with sample 4, the gas discharge effect and the like in the steps of discharging O ₂ gas and discharging NH ₃ gas, the step of discharging HCDS gas, and C ₃ H ₆ It is understood that the number of particles can be reduced in samples 1 to 3 in which the gas discharging effect or the like in the step of discharging the gas is larger than the sample 4. Also, comparing the above average values of the samples 1 and ₂ , in the steps of discharging the O ₂ gas and discharging the NH ₃ gas, the execution time of the exhaust treatment (VAC) and the purge treatment ( It can be seen that the number of particles can be reduced in sample 1 in which the PRG) execution time is extended, compared to sample 2. Further, comparing the above-mentioned average values of the samples 2 and ₃ , the number (m ₃ ) of cycle purge processing performed in the step of discharging the O ₂ gas and cycle purge processing performed in the step of discharging the NH ₃ gas It can be seen that the sample 3 in which the number of times of execution (m ₄ ) is increased can reduce the number of particles more than the sample 2.

<Preferred embodiment of the present invention>
Hereinafter, preferred embodiments of the present invention will be additionally stated.

(Supplementary Note 1)
According to one aspect of the invention:
Supplying a source gas to the substrate in the processing chamber;
Discharging the source gas from the processing chamber;
Supplying an oxygen-containing gas to the substrate in the processing chamber;
Discharging the oxygen-containing gas from the processing chamber;
Supplying a hydrogen-containing gas to the substrate in the processing chamber;
Discharging the hydrogen-containing gas from the processing chamber;
Forming a film on the substrate by performing a predetermined number of non-simultaneous cycles.
A method of manufacturing a semiconductor device, wherein at least one of the gas discharging effect and the efficiency in the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas is larger than that in the step of discharging the source gas Or, a substrate processing method is provided.

(Supplementary Note 2)
The method according to appendix 1, preferably
The gas discharge time in the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas is made longer than that in the step of discharging the source gas, or the step of discharging the oxygen-containing gas and the above The supply flow rate of the purge gas supplied into the processing chamber in the step of discharging the hydrogen-containing gas is made larger than that in the step of discharging the source gas.

(Supplementary Note 3)
The method according to supplementary note 1 or 2, preferably
In the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas, a step of evacuating the processing chamber without supplying the gas into the processing chamber, and supplying a purge gas into the processing chamber And (d) exhaust the room a predetermined number of times not simultaneously
In the step of discharging the source gas, a step of supplying a purge gas into the processing chamber (while exhausting the processing chamber) is performed, and a step of discharging the processing chamber without supplying the gas into the processing chamber is not performed. I assume. Note that the exhaust includes a reduced pressure exhaust.

(Supplementary Note 4)
The method according to any one of appendices 1 to 3, preferably
In the step of forming the film, at least a step of supplying the oxygen-containing gas, a step of discharging the oxygen-containing gas, a step of supplying the hydrogen-containing gas, and a step of discharging the hydrogen-containing gas In this order,
At least one of the gas discharge effect and the efficiency in the step of discharging the oxygen-containing gas is made greater than that in the step of discharging the hydrogen-containing gas.

(Supplementary Note 5)
It is a method as described in appendix 4, and preferably
Make the gas discharge time in the step of discharging the oxygen-containing gas longer than that in the step of discharging the hydrogen-containing gas, or
The supply flow rate of the purge gas supplied into the processing chamber in the step of discharging the oxygen-containing gas is made larger than that in the step of discharging the hydrogen-containing gas.

(Supplementary Note 6)
The method according to Supplementary Note 4 or 5, preferably
In the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas, a first step of evacuating the processing chamber without supplying the gas into the processing chamber, and supplying a purge gas into the processing chamber And the second step of evacuating the processing chamber a predetermined number of times not simultaneously.
The number of times the first step and the second step are performed in the step of discharging the oxygen-containing gas is made greater than the number of times the first step and the second step are performed in the step of discharging the hydrogen-containing gas . Note that the exhaust includes a reduced pressure exhaust.

(Appendix 7)
The method according to any one of appendices 1 to 3, preferably
In the step of forming the film, at least a step of supplying the hydrogen-containing gas, a step of discharging the hydrogen-containing gas, a step of supplying the oxygen-containing gas, and a step of discharging the oxygen-containing gas In this order,
At least one of the gas discharge effect and the efficiency in the step of discharging the hydrogen-containing gas is made greater than that in the step of discharging the oxygen-containing gas.

(Supplementary Note 8)
It is a method as described in appendix 7, and preferably
Make the gas discharge time in the step of discharging the hydrogen-containing gas longer than that in the step of discharging the oxygen-containing gas, or
The supply flow rate of the purge gas supplied into the processing chamber in the step of discharging the hydrogen-containing gas is made larger than that in the step of discharging the oxygen-containing gas.

(Appendix 9)
The method according to Supplementary Note 7 or 8, preferably
In the step of discharging the hydrogen-containing gas and the step of discharging the oxygen-containing gas, a first step of evacuating the processing chamber without supplying the gas into the processing chamber, and supplying a purge gas into the processing chamber And the second step of evacuating the processing chamber a predetermined number of times not simultaneously.
The number of times the first step and the second step are performed in the step of discharging the hydrogen-containing gas is made greater than the number of times the first step and the second step are performed in the step of discharging the oxygen-containing gas . Note that the exhaust includes a reduced pressure exhaust.

(Supplementary Note 10)
The method according to any one of appendices 1 to 9, preferably
At least the oxygen-containing gas and the hydrogen-containing gas are supplied to the substrate through the same nozzle.

(Supplementary Note 11)
The method according to any one of appendices 1 to 10, preferably
The source gas is supplied through a first nozzle,
Supplying the oxygen-containing gas via a second nozzle different from the first nozzle;
The hydrogen-containing gas is supplied through the second nozzle.

(Supplementary Note 12)
The method according to any one of appendices 1 to 11, preferably
The hydrogen-containing gas is a gas containing nitrogen and hydrogen.

(Supplementary Note 13)
The method according to any one of appendices 1 to 12, preferably
The cycle further comprises
Supplying a carbon-containing gas to the substrate in the processing chamber;
Discharging the carbon-containing gas from the processing chamber;
Performing the steps not simultaneously with the respective steps,
At least one of the gas discharging effect and the efficiency in the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas (the gas containing nitrogen and hydrogen), the step of discharging the source gas and the carbon-containing Make it larger than that in the process of discharging gas.

(Supplementary Note 14)
It is a method as described in appendix 13, and preferably
The gas discharge time in the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas (the gas containing the nitrogen and hydrogen), the step of discharging the source gas and the step in discharging the carbon-containing gas Alternatively, in the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas (the gas containing nitrogen and hydrogen), the feed flow rate of the purge gas supplied into the processing chamber is the source gas Discharging the carbon-containing gas and discharging the carbon-containing gas.

(Supplementary Note 15)
The method according to appendix 13 or 14, preferably
In the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas (the gas containing nitrogen and hydrogen), the step of exhausting the inside of the processing chamber without supplying the gas into the processing chamber; Supplying a purge gas to the chamber (while exhausting the processing chamber while performing the
In the step of discharging the source gas and the step of discharging the carbon-containing gas, a step of supplying a purge gas into the processing chamber (while exhausting the processing chamber while performing the purge gas) is performed, and the gas is not supplied into the processing chamber The process of evacuating the processing chamber is not performed. Note that the exhaust includes a reduced pressure exhaust.

(Supplementary Note 16)
The method according to any of Appendices 3, 6, 9 or 15, preferably
The execution time of the step of supplying the purge gas into the processing chamber (while exhausting the processing chamber) is shorter than the execution time of the step of exhausting the processing chamber without supplying the gas into the processing chamber.

(Supplementary Note 17)
According to another aspect of the invention,
Supplying a source gas to the substrate in the processing chamber;
Discharging the source gas from the processing chamber;
Supplying an oxygen-containing gas to the substrate in the processing chamber;
Discharging the oxygen-containing gas from the processing chamber;
Supplying a gas containing nitrogen and hydrogen to the substrate in the processing chamber;
Discharging the gas containing nitrogen and hydrogen from the processing chamber;
Forming a film on the substrate by performing a predetermined number of non-simultaneous cycles.
Semiconductor device in which at least one of gas exhaust effect and efficiency in the step of discharging the oxygen-containing gas and the step of discharging the gas containing nitrogen and hydrogen is larger than that in the step of discharging the source gas A method of manufacturing the substrate or a method of processing a substrate is provided.

(Appendix 18)
According to yet another aspect of the invention,
Supplying a source gas to the substrate in the processing chamber;
Discharging the source gas from the processing chamber;
Supplying a carbon-containing gas to the substrate in the processing chamber;
Discharging the carbon-containing gas from the processing chamber;
Supplying an oxygen-containing gas to the substrate in the processing chamber;
Discharging the oxygen-containing gas from the processing chamber;
Supplying a gas containing nitrogen and hydrogen to the substrate in the processing chamber;
Discharging the gas containing nitrogen and hydrogen from the processing chamber;
Forming a film on the substrate by performing a predetermined number of non-simultaneous cycles.
At least one of the gas discharging effect and the efficiency in the step of discharging the oxygen-containing gas and the step of discharging the gas containing nitrogen and hydrogen, the step of discharging the source gas and the step of discharging the carbon-containing gas There is provided a method of manufacturing a semiconductor device or a method of processing a substrate, which is larger than that.

(Appendix 19)
According to yet another aspect of the invention,
A processing chamber for containing a substrate;
A source gas supply system for supplying a source gas to a substrate in the processing chamber;
An oxygen-containing gas supply system for supplying an oxygen-containing gas to a substrate in the processing chamber;
A hydrogen-containing gas supply system for supplying a hydrogen-containing gas to a substrate in the processing chamber;
An exhaust system for exhausting the gas in the processing chamber;
A process of supplying the source gas to a substrate in the process chamber, a process of discharging the source gas from the process chamber, a process of delivering the oxygen-containing gas to the substrate in the process chamber, and The process of discharging the oxygen-containing gas from the process chamber, the process of supplying the hydrogen-containing gas to the substrate in the process chamber, and the process of discharging the hydrogen-containing gas from the process chamber are not performed simultaneously A process of forming a film on the substrate is performed by performing a predetermined number of cycles, and at least one of a gas discharge effect and an efficiency in the process of discharging the oxygen-containing gas and the process of discharging the hydrogen-containing gas, The source gas supply system, the oxygen-containing gas supply system, the hydrogen-containing gas, and the hydrogen-containing gas supply system to make the source gas larger than that in the process of discharging the source gas When configured controller to control the scan supply system, and the exhaust system,
A substrate processing apparatus is provided.

(Supplementary Note 20)
According to yet another aspect of the invention,
Supplying a source gas to the substrate in the processing chamber;
A step of discharging the source gas from the processing chamber;
Supplying an oxygen-containing gas to the substrate in the processing chamber;
A step of discharging the oxygen-containing gas from the processing chamber;
Supplying a hydrogen-containing gas to the substrate in the processing chamber;
A step of discharging the hydrogen-containing gas from the processing chamber;
Causing a computer to execute a procedure of forming a film on the substrate by performing a predetermined number of non-simultaneous cycles.
A program for increasing at least one of the gas discharge effect and the efficiency in the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas, or higher than that in the step of discharging the source gas; A computer readable recording medium having a program recorded thereon is provided.

121 controller (control unit)
200 wafers (substrate)
201 processing chamber 202 processing furnace 203 reaction tube 207 heater 231 exhaust tube 232a to 232d gas supply tube

Claims (14)

Supplying a source gas to the substrate in the processing chamber;
Discharging the source gas from the processing chamber;
Supplying an oxygen-containing gas to the substrate in the processing chamber;
Discharging the oxygen-containing gas from the processing chamber;
Supplying a hydrogen-containing gas to the substrate in the processing chamber;
Discharging the hydrogen-containing gas from the processing chamber;
Forming a film on the substrate by performing a predetermined number of non-simultaneous cycles.
In the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas, a first step of exhausting the processing chamber without supplying the gas into the processing chamber, and a second step of supplying a purge gas into the processing chamber Perform the steps a predetermined number of times simultaneously
The method of manufacturing a semiconductor device, wherein, in the step of discharging the source gas, a third step of exhausting the purge gas from the processing chamber while supplying the purge gas to the processing chamber is performed. Making the gas discharge time in the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas longer than that in the step of discharging the source gas, or
The semiconductor according to claim 1, wherein the supply flow rate of the purge gas supplied into the processing chamber in the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas is larger than that in the step of discharging the source gas. Device manufacturing method. In the step of forming the film, at least a step of supplying the oxygen-containing gas, a step of discharging the oxygen-containing gas, a step of supplying the hydrogen-containing gas, and a step of discharging the hydrogen-containing gas In this order,
Make the gas discharge time in the step of discharging the oxygen-containing gas longer than that in the step of discharging the hydrogen-containing gas, or
3. The method of manufacturing a semiconductor device according to claim 1, wherein the supply flow rate of the purge gas supplied into the processing chamber in the step of discharging the oxygen-containing gas is larger than that in the step of discharging the hydrogen-containing gas. In the step of forming the film, at least a step of supplying the oxygen-containing gas, a step of discharging the oxygen-containing gas, a step of supplying the hydrogen-containing gas, and a step of discharging the hydrogen-containing gas In this order,
The number of times the first step and the second step are performed in the step of discharging the oxygen-containing gas is made greater than the number of times the first step and the second step are performed in the step of discharging the hydrogen-containing gas A method of manufacturing a semiconductor device according to claim 1. In the step of forming the film, at least a step of supplying the hydrogen-containing gas, a step of discharging the hydrogen-containing gas, a step of supplying the oxygen-containing gas, and a step of discharging the oxygen-containing gas In this order,
Make the gas discharge time in the step of discharging the hydrogen-containing gas longer than that in the step of discharging the oxygen-containing gas, or
3. The method of manufacturing a semiconductor device according to claim 1, wherein a supply flow rate of the purge gas supplied into the processing chamber in the step of discharging the hydrogen-containing gas is made larger than that in the step of discharging the oxygen-containing gas. In the step of forming the film, at least a step of supplying the hydrogen-containing gas, a step of discharging the hydrogen-containing gas, a step of supplying the oxygen-containing gas, and a step of discharging the oxygen-containing gas In this order,
The number of times the first step and the second step are performed in the step of discharging the hydrogen-containing gas is made greater than the number of times the first step and the second step are performed in the step of discharging the oxygen-containing gas A method of manufacturing a semiconductor device according to claim 1.   The method for manufacturing a semiconductor device according to any one of claims 1 to 6, wherein at least the oxygen-containing gas and the hydrogen-containing gas are supplied to the substrate through the same nozzle. The source gas is supplied through a first nozzle,
Supplying the oxygen-containing gas via a second nozzle different from the first nozzle;
The method of manufacturing a semiconductor device according to claim 1, wherein the hydrogen-containing gas is supplied through the second nozzle.   The method for manufacturing a semiconductor device according to claim 1, wherein the hydrogen-containing gas is a gas containing nitrogen and hydrogen. The cycle further comprises
Supplying a carbon-containing gas to the substrate in the processing chamber;
Discharging the carbon-containing gas from the processing chamber;
Performing the steps not simultaneously with the respective steps,
The gas discharge time in the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas is made longer than that in the step of discharging the carbon-containing gas, or the step of discharging the oxygen-containing gas The semiconductor device according to any one of claims 1 to 9, wherein the supply flow rate of the purge gas supplied into the processing chamber in the step of discharging the hydrogen-containing gas is larger than that in the step of discharging the carbon-containing gas. Manufacturing method. The cycle further comprises
Supplying a carbon-containing gas to the substrate in the processing chamber;
Discharging the carbon-containing gas from the processing chamber;
Performing the steps not simultaneously with the respective steps,
The method of manufacturing a semiconductor device according to any one of claims 1 to 9, wherein the third step is performed in the step of discharging the carbon-containing gas.   The method of manufacturing a semiconductor device according to any one of claims 1 to 11, wherein an execution time of the second step is made shorter than an execution time of the first step. A processing chamber for containing a substrate;
A gas supply system for supplying a gas to a substrate in the processing chamber;
An exhaust system for exhausting the gas in the processing chamber;
A process of supplying a source gas to a substrate in the process chamber, a process of discharging the source gas from the process chamber, a process of delivering an oxygen-containing gas to the substrate in the process chamber, the process chamber Predetermined cycle for performing the process of discharging the oxygen-containing gas from the chamber, the process of supplying the hydrogen-containing gas to the substrate in the processing chamber, and the process of discharging the hydrogen-containing gas from the processing chamber at the same time By performing the process of forming a film on the substrate by performing the process several times, in the process of discharging the oxygen-containing gas and the process of discharging the hydrogen-containing gas, the inside of the processing chamber is supplied without supplying the gas into the processing chamber. The first process for exhausting the gas and the second process for supplying the purge gas into the processing chamber are performed a predetermined number of times at the same time, and in the process for discharging the source gas, the purge gas is supplied to the processing chamber To perform the third processing for exhausting from the process chamber while supplying the configured control unit to control the gas supply system and the exhaust system,
Substrate processing apparatus having: A step of supplying a source gas to a substrate in a processing chamber of the substrate processing apparatus;
A step of discharging the source gas from the processing chamber;
Supplying an oxygen-containing gas to the substrate in the processing chamber;
A step of discharging the oxygen-containing gas from the processing chamber;
Supplying a hydrogen-containing gas to the substrate in the processing chamber;
A step of discharging the hydrogen-containing gas from the processing chamber;
Causing the substrate processing apparatus to execute a procedure of forming a film on the substrate by performing a predetermined number of cycles of nonconcurrently performing
In the step of discharging the oxygen-containing gas and the step of discharging the hydrogen-containing gas, a first step of exhausting the processing chamber without supplying the gas into the processing chamber, and a second step of supplying a purge gas into the processing chamber Do not execute the procedure a predetermined number of times at the same time
In the procedure of discharging the source gas, a program for performing a third procedure of exhausting the purge gas from the processing chamber while supplying the purge gas to the processing chamber.

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