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

Abstract

The invention relates to a substrate processing method, a semiconductor device manufacturing method, a recording medium, and a substrate processing apparatus. Provided is a technique capable of improving the characteristics of a film formed on a substrate. The method comprises: (a) a step for supplying a substrate with a non-reducing accelerator that promotes adsorption of a modifier containing an organic ligand; (b) a step for supplying the modifying agent to the substrate; and (c) a step for forming a film on the substrate after performing (a) and (b).

Description

Technical Field

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

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

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2022-50996 Summary of the invention

[0006] Problems to be solved by the invention

[0007] When a film is formed on a substrate, the continuity of the film may be reduced, and the characteristics of the film formed on the substrate may be deteriorated.

[0008] The present invention provides a technology capable of improving the characteristics of a film formed on a substrate.

[0009] Means for solving problems

[0010] According to one embodiment of the present invention, a technology is provided, which has:

[0011] (a) supplying a non-reducing promoter to the substrate to promote adsorption of a modifier containing an organic ligand;

[0012] (b) supplying the modifying agent to the substrate; and

[0013] (c) After performing (a) and (b), a step of forming a film on the aforementioned substrate.

[0014] Effects of the Invention

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

[0016] [ Figure 1 ] is a schematic longitudinal sectional view showing a vertical processing furnace of a substrate processing device in one embodiment of the present invention.

[0017] [ Figure 2 ]for Figure 1 Schematic cross-section diagram along line AA.

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

[0019] [ Figure 4 ] is a diagram showing a substrate processing sequence according to one embodiment of the present invention.

[0020] [ Figure 5 ] is a top view showing a modified example of a substrate processing device in one embodiment of the present invention.

[0021] Description of Reference Numerals

[0022] 200 wafers (substrate) DETAILED DESCRIPTION

[0023] The following are the main references Figure 1 to Figure 4 One embodiment of the present invention is described. It should be noted that the drawings used in the following description are all schematic, and the dimensional relationship of each element, the ratio of each element, etc. shown in the drawings are not necessarily consistent with the actual ones. In addition, the dimensional relationship of each element, the ratio of each element, etc. are not necessarily consistent between multiple drawings.

[0024] (1) Configuration of substrate processing apparatus

[0025] like Figure 1 As shown, the processing furnace 202 has a heater 207 as a heating system (temperature adjustment unit). The heater 207 has a cylindrical shape. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) the gas by heat.

[0026] On the inner side of the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal such as stainless steel (SUS), and is formed into a cylindrical shape with an upper end and a lower end open. The upper end of the manifold 209 is engaged with the lower end of the reaction tube 203, and is configured in a manner to support the reaction tube 203. An O-ring 220a as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically in the same manner as the heater 207. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow portion of the cylinder of the processing container. The processing chamber 201 is configured to accommodate a plurality of wafers 200 as substrates.

[0027] In the processing chamber 201, nozzles 249a and 249b are provided so as to penetrate the side wall of the manifold 209. Gas supply pipes (pipes) 232a and 232b are connected to the nozzles 249a and 249b, respectively.

[0028] The gas supply pipes 232a and 232b are provided with mass flow controllers (MFC) 241a and 241b as flow controllers (flow control units) and valves 243a and 243b as opening and closing valves, respectively, in order from the upstream side. The gas supply pipes 232c and 232e are connected to the downstream side of the gas supply pipe 232a relative to the valve 243a. The gas supply pipes 232c and 232e are provided with MFCs 241c and 241e and valves 243c and 243e, respectively, in order from the upstream side. The gas supply pipes 232d and 232f are connected to the downstream side of the gas supply pipe 232b relative to the valve 243b. The gas supply pipes 232d and 232f are provided with MFCs 241d and 241f and valves 243d and 243f, respectively, in order from the upstream side.

[0029] like Figure 2 As shown, in the annular space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, nozzles 249a and 249b are respectively provided in a manner of standing upright from the lower part of the inner wall of the reaction tube 203 along the upper part toward the upper part of the loading direction of the wafer 200. Gas supply holes 250a and 250b for supplying gas are respectively provided on the side of the nozzles 249a and 249b. The gas supply holes 250a and 250b are respectively opened in a manner of facing the center of the reaction tube 203, and can supply gas to the wafer 200. A plurality of gas supply holes 250a and 250b are provided in the range from the lower part to the upper part of the reaction tube 203.

[0030] A source gas containing a halogen element is supplied into the processing chamber 201 from the gas supply pipe 232 a via the MFC 241 a , the valve 243 a , and the nozzle 249 a .

[0031] A reaction gas containing hydrogen element is supplied into the processing chamber 201 from the gas supply pipe 232 b via the MFC 241 b , the valve 243 b , and the nozzle 249 b .

[0032] An accelerator for accelerating adsorption of the reforming agent is supplied from the gas supply pipe 232c via the MFC 241c, the valve 243c, and the nozzle 249a into the processing chamber 201. As the accelerator, an accelerator having no reducing property is used.

[0033] It should be noted that the term "agent" used in this specification includes at least one of a gaseous substance and a liquid substance. A liquid substance includes a mist substance. That is, a modifier or a promoter may include a gaseous substance, a liquid substance such as a mist substance, or both.

[0034] A reforming agent including an organic ligand is supplied into the processing chamber 201 from the gas supply pipe 232 d via the MFC 241 d , the valve 243 d , and the nozzle 249 b .

[0035] An inert gas is supplied into the processing chamber 201 from the gas supply pipes 232e and 232f via the MFCs 241e and 241f, valves 243e and 243f, the gas supply pipes 232a and 232b, and the nozzles 249a and 249b, respectively.

[0036] The raw gas supply system is mainly composed of a gas supply pipe 232a, MFC241a, and valve 243a. The reaction gas supply system is mainly composed of a gas supply pipe 232b, MFC241b, and valve 243b. The raw gas supply system and the reaction gas supply system can also be collectively referred to as a gas supply system. In addition, the accelerator supply system as the first gas supply system is mainly composed of a gas supply pipe 232c, MFC241c, and valve 243c. The modifier supply system as the second gas supply system is mainly composed of a gas supply pipe 232d, MFC241d, and valve 243d. In addition, the inert gas supply system is mainly composed of gas supply pipes 232e, 232f, MFC241e, 241f, valves 243e, and 243f. It is also conceivable to include the accelerator supply system, the modifier supply system, and the inert gas supply system in the gas supply system.

[0037] Any or all of the above-mentioned various supply systems can be configured as an integrated supply system 248 in which valves 243a to 243f, MFCs 241a to 241f, etc. are integrated. The integrated supply system 248 is connected to the gas supply pipes 232a to 232f, respectively, and is configured so that the controller 121 described later controls the operation of supplying various gases into the gas supply pipes 232a to 232f, that is, the opening and closing operation of the valves 243a to 243f, the flow rate adjustment operation performed by the MFCs 241a to 241f, etc. The integrated supply system 248 is configured in the form of an integrated unit of an integral type or a split type, and is configured so that the gas supply pipes 232a to 232f, etc. can be installed and removed as an integrated unit, and the integrated supply system 248 can be maintained, replaced, and added as an integrated unit.

[0038] The reaction tube 203 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201. A vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure regulation unit). The APC valve 244 is configured to enable vacuum exhaust and stop of the processing chamber 201 by opening and closing the valve in a state where the vacuum pump 246 is in operation. In addition, the pressure in the processing chamber 201 can be adjusted by adjusting the valve opening based on the pressure information detected by the pressure sensor 245 in a state where the vacuum pump 246 is in operation. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. It is also conceivable to include the vacuum pump 246 in the exhaust system.

[0039] Below the manifold 209, a sealing cover 219 as a furnace port cover that can airtightly close the lower end opening of the reaction tube 203 is provided. The sealing cover 219 is made of metal such as SUS and is formed in a disc shape. On the upper surface of the sealing cover 219, an O-ring 220b as a sealing member that abuts against the lower end of the manifold 209 is provided. Below the sealing cover 219, a rotating mechanism 267 for rotating the wafer boat 217 described later is provided. The rotating shaft 255 of the rotating mechanism 267 penetrates the sealing cover 219 and is connected to the wafer boat 217. The rotating mechanism 267 is configured in such a way that the wafer 200 is rotated by rotating the wafer boat 217. The sealing cover 219 is configured in such a way that it is lifted and lowered in the vertical direction by the wafer boat elevator 115 as a lifting mechanism provided outside the reaction tube 203. The boat elevator 115 is configured to be able to carry the boat 217 into and out of the processing chamber 201 by raising and lowering the sealing cover 219. The boat elevator 115 is configured as a transport device (transport mechanism) that carries the boat 217, i.e., the wafers 200 into and out of the processing chamber 201.

[0040] The wafer boat 217 as a substrate support is constructed in a manner that a plurality of (for example, 25 to 200) wafers 200 are arranged in a horizontal posture and in a state where the centers are aligned with each other in the vertical direction and supported in multiple layers, that is, arranged at intervals. The wafer boat 217 is made of a heat-resistant material such as quartz, SiC, etc. In the lower part of the wafer boat 217, a heat insulation plate 218 made of a heat-resistant material such as quartz, SiC, etc. is supported in multiple layers. It should be noted that the expression of a numerical range such as "25 to 200 sheets" in this specification means that the lower limit and the upper limit are included in the range. Therefore, for example, the so-called "25 to 200 sheets" means "more than 25 sheets and less than 200 sheets". The same is true for other numerical ranges.

[0041] A temperature sensor 263 as a temperature detector is provided in the reaction tube 203. The temperature in the processing chamber 201 is set to a desired temperature distribution by adjusting the power supply state to the heater 207 based on the temperature information detected by the temperature sensor 263. The temperature sensor 263 is configured in an L shape and is provided along the inner wall of the reaction tube 203.

[0042] like Figure 3 As shown, the controller 121 as a control unit (control means) is configured in the form of a computer having a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. RAM 121b, a storage device 121c, and an I / O port 121d are configured to be able to exchange data with CPU 121a via an internal bus 121e. An input and output device 122 such as a touch panel is connected to the controller 121. It should be noted that the substrate processing device can be configured in a manner having one control unit or in a manner having multiple control units. That is, one control unit can be used to control the processing sequence described later, or multiple control units can be used to control the processing sequence described later. In addition, multiple control units can be configured as a control system connected to each other through a wired or wireless communication network, or the control system as a whole can be used to control the processing sequence described later. In this specification, the term "control unit" includes a case where one control unit is included, a case where a plurality of control units are included, and a case where a control system composed of a plurality of control units is included.

[0043] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), etc. In the storage device 121c, a control program for controlling the action of the substrate processing device 100, a process process recording the steps, conditions, etc. of the substrate processing described later, etc. are stored in a readable manner. The process process is a combination of a method that enables the controller 121 to execute each step in the substrate processing described later and obtain a specified result, and functions as a program. Hereinafter, the process process, the control program, etc. are also simply referred to as a program. In addition, the process process is also referred to as a process. In this specification, the use of the term program includes a case where only the process is included, a case where only the control program is included, or a case where both are included. RAM121b is configured as a storage area (work area) for temporarily holding programs, data, etc. read by CPU121a.

[0044] The I / O port 121 d is connected to the above-mentioned MFCs 241 a to 241 f , valves 243 a to 243 f , pressure sensor 245 , APC valve 244 , vacuum pump 246 , heater 207 , temperature sensor 263 , rotation mechanism 267 , boat elevator 115 , and the like.

[0045] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a process from the storage device 121c according to input of an operation command from the input / output device 122. The CPU 121a is configured to control the following actions according to the contents of the read process: flow rate adjustment actions of various gases by the MFCs 241a to 241f, opening and closing actions of the valves 243a to 243f, opening and closing actions of the APC valve 244 and pressure adjustment actions by the APC valve 244 based on the pressure sensor 245, starting and stopping of the vacuum pump 246, temperature adjustment actions of the heater 207 by the temperature sensor 263, rotation of the wafer boat 217 by the rotating mechanism 267 and adjustment actions of the rotation speed, and lifting and lowering actions of the wafer boat 217 by the wafer boat elevator 115, etc.

[0046] The controller 121 can be constructed by installing the above-mentioned program stored in an external storage device (for example, a magnetic disk such as a hard disk, an optical disk such as a CD, an optical magnetic disk such as an MO, a semiconductor memory such as a USB memory) 123 in a computer. The storage device 121c and the external storage device 123 are constructed in the form of a computer-readable recording medium that records the program. Hereinafter, they are also simply collectively referred to as recording media. In this specification, the use of the term recording medium includes a case where only the storage device 121c is included alone, a case where only the external storage device 123 is included alone, or a case where both are included. It should be noted that providing the program to the computer can also be carried out without using the external storage device 123 and using communication means such as the Internet and dedicated lines.

[0047] (2) Substrate processing step

[0048] As an example of a process of forming a thin film on a wafer 200 as one of the processes of manufacturing a semiconductor device (Device), a Figure 4 In the following description, the operations of the various components constituting the substrate processing apparatus 100 are controlled by the controller 121 .

[0049] The term "wafer" used in this specification includes the case where it refers to the wafer itself, and the case where it refers to a stack of a wafer and a predetermined layer or film formed on its surface. The term "surface of the wafer" used in this specification includes the case where it refers to the surface of the wafer itself, and the case where it refers to the surface of a predetermined layer, etc. formed on the wafer. In this specification, the case where "a predetermined layer is formed on the wafer" includes the case where a predetermined layer is directly formed on the surface of the wafer itself, and the case where a predetermined layer is formed on a layer, etc. formed on the wafer. In this specification, the case where the term "substrate" is used has the same meaning as the case where the term "wafer" is used.

[0050] (Wafer loading)

[0051] When a plurality of wafers 200 are loaded (wafer filling) into the wafer boat 217, as shown in FIG. Figure 1 As shown, the boat 217 supporting a plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat loading) and stored in the processing container. In this state, the sealing cap 219 is in a state of closing the lower end opening of the manifold 209 via the O-ring 220b.

[0052] (Pressure regulation and temperature regulation)

[0053] The vacuum pump 246 is used to perform vacuum exhaust so that the space in the processing chamber 201, that is, the space where the wafer 200 exists, becomes 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 (pressure regulated) based on the measured pressure information. The vacuum pump 246 is always kept in an operating state at least until the processing of the wafer 200 is completed. In addition, the heater 207 is used to heat the processing chamber 201 so that the temperature inside the processing chamber 201 becomes a desired temperature. At this time, the amount of power supplied to the heater 207 is feedback-controlled (temperature regulated) based on the temperature information detected by the temperature sensor 263 so that the temperature distribution inside the processing chamber 201 becomes a desired temperature distribution. The heating in the processing chamber 201 by the heater 207 is continuously performed at least until the processing of the wafer 200 is completed.

[0054] [Pre-process]

[0055] (Promoter supply in time; step 1)

[0056] First, in this step, the accelerator is supplied in a time-sharing manner. In other words, the accelerator is supplied for a predetermined number of times (one or more times, preferably multiple times). Specifically, the accelerator supply process of opening the valve 243c and supplying the accelerator into the gas supply pipe 232c, and the accelerator removal process of closing the valve 243c and stopping the supply of the accelerator and removing the accelerator in the processing chamber 201 are sequentially performed for a predetermined number of times (p times, where p is an integer greater than 1 or 2). That is, the supply and stop of the accelerator (also called exhaustion or purging) are alternately performed in a time-sharing manner.

[0057] In the accelerator supply process, the accelerator is flow-regulated by MFC241c, supplied from nozzle 249a to the processing chamber 201, and exhausted from exhaust pipe 231. At this time, valve 243e may be opened at the same time to flow inert gas into gas supply pipe 232e. In addition, in order to prevent the accelerator from invading nozzle 249b, valve 243f may be opened to flow inert gas into gas supply pipe 243b. In addition, in the accelerator removal process, APC valve 244 of exhaust pipe 231 is kept in an open state, vacuum pump 246 is used to vacuum exhaust the processing chamber 201, the accelerator is removed from the wafer 200, and the unreacted accelerator and reaction by-products remaining in the processing chamber 201 are discharged from the processing chamber 201. At this time, valves 243e and 243f are kept in an open state to maintain the supply of inert gas as a purge gas into the processing chamber 201.

[0058] It should be noted that, in this specification, the term "time-sharing" means being divided (separated) in time. For example, in this specification, the term "time-sharing supply of the accelerator" means not supplying the accelerator continuously. In other words, it means supplying the accelerator in a pulsed manner. It should be noted that the accelerator may also be supplied intermittently.

[0059] At this time, the main gas supplied in a time-division manner in the processing chamber 201 is an accelerator. By supplying the accelerator to the wafer 200 in a plurality of times in this manner, the accelerator can be adsorbed onto the wafer 200 without any gap.

[0060] As a promoter, a non-reducing, oxidizing gas can be used. As an oxidizing gas, for example, oxygen (O2) gas, ozone (O3) gas, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, hydrogen (H2) gas + O2 gas, etc. can be used. As a promoter, a gas activated by one or more of them can be used. As an activated gas, there is a gas activated by plasma or heat. The following is the same.

[0061] It should be noted that, in this specification, the parallel description of two gases such as "H2 gas + O2 gas" means a mixed gas of H2 gas and O2 gas. When supplying a mixed gas, the two gases can be mixed (pre-mixed) in a supply pipe and then supplied to the processing chamber 201, or the two gases can be supplied to the processing chamber 201 separately through different supply pipes and mixed (post-mixed) in the processing chamber 201.

[0062] In addition, as a promoter, an oxidizing gas that does not contain hydrogen (H) can be used. As the oxidizing gas that does not contain H, for example, O2 gas, O3 gas, etc. can be used. As a promoter, a gas obtained by activating one or more of these can be used.

[0063] As the inert gas, for example, in addition to nitrogen (N2) gas, rare gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas can be used. As the inert gas, one or more of them can be used.

[0064] By supplying a promoter, atoms and molecules that promote the adsorption of a modifier containing an organic ligand are adsorbed on the chip 200 (the base film on the surface). Specifically, by supplying, for example, an oxidizing gas as a promoter, oxygen radicals (hereinafter referred to as O-) and O2 are adsorbed on the chip 200. That is, the surface of the chip 200 is capped with O- and O2. It should be noted that in the present invention, the so-called "capping" and "adsorption" may also include a state in which the surface of the chip 200 is not completely covered. Sometimes, depending on the supply conditions of the gas and the surface state of the chip 200, the surface of the chip 200 is not completely covered. In addition, sometimes, the reaction stops due to self-limitation and is not completely covered. In the present invention, by supplying a promoter multiple times, the amount of the promoter adsorbed on the chip 200 can be increased. In other words, the promoter can be adsorbed on nearly all adsorption sites to which the promoter can be adsorbed.

[0065] In the first step, the pressure of the space above the chip 200 (processing chamber 201) is set to a pressure in the range of, for example, 1 to 3990 Pa. The supply flow rate of the accelerator controlled by MFC241c is set to a flow rate in the range of, for example, 0.01 to 5.0 slm. Hereinafter, with regard to the temperature of the heater 207, the temperature is set in such a manner that the temperature of the chip 200 becomes, for example, a temperature in the range of 300 to 550°C. It should be noted that the expression of a numerical range such as "1 to 3990 Pa" in the present invention means that the lower limit and the upper limit are included in the range. Therefore, for example, the so-called "1 to 3990 Pa" means "above 1 Pa and below 3990 Pa". The same is true for other numerical ranges.

[0066] (Purge; Step 2)

[0067] After a predetermined time has passed since the start of the time-sharing supply of the accelerator, the valve 243c is closed to stop the supply of the accelerator. At this time, the APC valve 244 of the exhaust pipe 231 is kept in an open state, and the processing chamber 201 is evacuated by the vacuum pump 246 to remove the residual gas from the wafer 200, and the unreacted accelerator and reaction by-products remaining in the processing chamber 201 are discharged from the processing chamber 201. At this time, the valves 243e and 243f are kept in an open state to maintain the supply of the inert gas as a purge gas into the processing chamber 201. The inert gas acts as a purge gas to remove the residual gas from the wafer 200, which can improve the effect of discharging the unreacted accelerator and reaction by-products remaining in the processing chamber 201 from the processing chamber 201.

[0068] In the second step, the supply flow rate of the inert gas controlled by the MFCs 241 e and 241 f is set to, for example, 0.1 to 10 slm.

[0069] (Supply of Modifier, Step 3)

[0070] The valve 243d is opened to flow the reformer into the gas supply pipe 232d. The reformer is flow-regulated by the MFC 241d, supplied into the processing chamber 201 from the gas supply hole 250b of the nozzle 249b, and exhausted from the exhaust pipe 231. At this time, the valve 243f may be opened at the same time to flow an inactive gas into the gas supply pipe 232f. In addition, in order to prevent the reformer from invading the nozzle 249a, the valve 243e may be opened to flow an inactive gas into the gas supply pipe 232e.

[0071] At this time, the main gas flowing in the processing chamber 201 is the modifier, that is, the modifier is supplied to the wafer 200 .

[0072] As the modifying agent, a gas containing an organic ligand, that is, a gas containing an organic compound can be used. As the gas containing an organic compound, a gas containing, for example, a hydrocarbon group (CH-), an amine group (NH-), etc. can be used.

[0073] As a gas containing an organic compound, a gas containing no metal element can be used. As a gas containing no metal element, a gas containing at least any one selected from the group consisting of an ether compound, a ketone compound, an amine compound including an amine, and an organic hydrazine compound can be used. As a gas containing an ether compound, a gas containing at least any one of dimethyl ether, diethyl ether, methyl ethyl ether, propyl ether, isopropyl ether, furan, tetrahydrofuran, pyran, tetrahydropyran, etc. can be used. As a gas containing a ketone compound, a gas containing at least any one of dimethyl ketone, diethyl ketone, methyl ethyl ketone, methyl propyl ketone, etc. can be used. As a gas containing an amine compound, a gas containing at least any one of monomethylamine (also referred to as CH3NH2, methylamine), methylamine compounds such as dimethylamine, trimethylamine, ethylamine compounds such as monoethylamine, diethylamine, triethylamine, dimethylethylamine, methyldiethylamine, etc. can be used. As a gas containing an organic hydrazine compound, a gas containing at least any one of methylhydrazine-based gases such as monomethylhydrazine, dimethylhydrazine, and trimethylhydrazine can be used. As the modifier, one or more of these may be used.

[0074] In addition, as the gas containing an organic compound, a gas containing a metal element can be used. As the gas containing a metal element, trimethylaluminum ((CH3)3Al) gas, trimethylgallium ((CH3)3Ga) gas, trimethylindium ((CH3)3In) gas, etc. can be used. As the modifier, one or more of them can be used.

[0075] By supplying the modifier, a part of the modifier reacts with O-, O2, etc. on the wafer 200 to generate reaction byproducts such as H2O, and hydrocarbon groups and amine groups such as alkyl groups such as methyl (CH3-), ethyl (C2H5-), propyl, isopropyl, etc. are adsorbed. By supplying the modifier, the adsorption amount of hydrocarbon groups and amine groups on the wafer 200 can be increased. In addition, in the film forming process described later, by supplying the raw material gas to the wafer 200 adsorbed with hydrocarbon groups and amine groups, the halogen elements contained in the raw material gas react with the hydrocarbon groups and amine groups present on the wafer 200, and molecules with a smaller number of molecules and less steric hindrance than the raw material gas are adsorbed on the wafer 200, forming a continuous film with a large adsorption amount of the raw material elements on the wafer 200.

[0076] Specifically, when O2 gas, which is an oxidizing gas, is used as a promoter, and CH3NH2 gas, which is a modifier, is used, O and O2 adsorbed on the wafer 200 react with CH3NH2 by the supply of CH3NH2 gas, and O and O2 are separated from the wafer 200 to generate H2O and be discharged. In addition, hydrocarbon groups and amine groups such as (CH3)-, (CH3)N-, and (CH3)NH- are adsorbed on the wafer 200 and remain. At this time, O and O2 may partially remain on the wafer 200, but since they exist at the interface between the oxide film of the base and the film formed in the film forming process described later, it is considered that the influence on the device characteristics is small. Furthermore, when titanium tetrachloride (TiCl4) gas is used as the raw material gas, for example, Cl contained in the TiCl4 gas reacts with (CH3)-, (CH3)N-, (CH3)NH-, etc. on the wafer 200 in the film forming process described later, and is detached from the wafer 200 in the form of (CH3)Cl, (CH3)NCl, (CH3)NHCl and discharged. That is, the generation of reaction by-products such as hydrogen chloride (HCl) that hinder the adsorption of the raw material elements is suppressed.

[0077] In the third step, the pressure of the processing chamber 201 is set to, for example, a pressure in the range of 1 to 3990 Pa. The supply flow rate of the reforming agent controlled by the MFC 241 d is set to, for example, a flow rate in the range of 0.01 to 5.0 slm.

[0078] (Purge; Step 4)

[0079] After a specified time has passed since the start of the supply of the modifier, valve 243d is closed to stop the supply of the modifier. At this time, the APC valve 244 of the exhaust pipe 231 is kept in an open state, and the vacuum pump 246 is used to vacuum exhaust the processing chamber 201, remove the residual gas from the wafer 200, and discharge the unreacted modifier and reaction by-products remaining in the processing chamber 201 from the processing chamber 201. At this time, valves 243e and 243f are kept in an open state to maintain the supply of inert gas as a purge gas into the processing chamber 201. The supply amount of the inert gas supplied in step 4 can be set to the same as that in step 2. In addition, the purge amount (supply amount of inert gas) can be appropriately adjusted according to the residual gas in the processing chamber 201. Here, the so-called supply amount refers to either or both of the supply flow rate and supply time set by the MFC.

[0080] (Perform a specified number of times; Step 5)

[0081] By performing the cycle of the above-mentioned steps 1 to 4 in sequence for a predetermined number of times (m times, m is an integer greater than or equal to 1 or 2), hydrocarbon groups, amine groups, etc. are adsorbed on the wafer 200. Here, for example, hydrocarbon groups and amine groups such as (CH3)-, (CH3)N-, and (CH3)NH- are adsorbed on the wafer 200. Thus, in the film forming process described later, the generation of reaction by-products such as HCl that hinder the adsorption of the raw material elements is suppressed by the supply of the raw material gas and the reaction gas.

[0082] For convenience, the processing in the above-mentioned pre-process may be shown as follows. The same symbols are also used in the following descriptions of other embodiments, etc. Here, "→" means to perform in sequence.

[0083] ((promoter supply→purge)×p→purge→modifier→purge)×m

[0084] (m and p are each an integer greater than 1 or 2)

[0085] It should be noted that although an example of supplying the modifier only once is shown, the present invention is not limited thereto, and the modifier may be supplied in the form of (modifier supply → purge)×o (where o is an integer greater than or equal to 1 or 2). By setting o to be greater than or equal to 2, the amount of the modifier adsorbed on the surface of the wafer 200 can be increased. In addition, by performing purge, byproducts generated when supplying the modifier can be removed from the space where the wafer 200 is present, and the amount of the modifier reaching the surface of the wafer 200 can be increased.

[0086] [Film forming process]

[0087] After the above-mentioned pre-process is performed, the following film forming process of forming a film on the wafer 200 is performed.

[0088] (Raw material gas supply; step 6)

[0089] The valve 243a is opened to allow the raw material gas to flow into the gas supply pipe 232a. The raw material gas is flow-regulated by the MFC 241a, supplied into the processing chamber 201 from the gas supply hole 250a of the nozzle 249a, and exhausted from the exhaust pipe 231. At this time, the valve 243e may be opened at the same time to allow the inert gas to flow into the gas supply pipe 232e. At this time, in order to prevent the raw material gas from invading the nozzle 249b, the valve 243f may be opened to allow the inert gas to flow into the gas supply pipe 232f.

[0090] At this time, the main gas flowing in the processing chamber 201 is the raw material gas, that is, the raw material gas is supplied to the wafer 200 .

[0091] As the raw material gas, a gas containing a halogen element can be used. As the gas containing a halogen element, a gas containing at least any one of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), etc. can be used. As the raw material gas, one or more of them can be used.

[0092] In addition, as the raw material gas, a gas containing a halogen element and a metal element can be used. Here, the metal element is set to be an element including at least one of the transition metals of the Group 3 to Group 12 elements, the Group 13 elements (such as aluminum (Al), gallium (Ga), indium (In)), silicon (Si), etc.

[0093] As a gas containing a halogen element and a Group 13 element, for example, aluminum chloride (AlCl3) gas can be used. As a gas containing a halogen element and Si, for example, silicon tetrachloride (SiCl4) gas, dichlorosilane (SiH2Cl2) gas, hexachlorodisilane (Si2Cl6) gas can be used.

[0094] As the gas containing halogen elements and transition metals, a gas containing halogen elements and at least one of Group 3 elements such as yttrium (Y) and lanthanum (La), Group 4 elements such as cerium (Ce), titanium (Ti), zirconium (Zr), and hafnium (Hf), Group 5 elements, and Group 6 elements such as chromium (Cr), molybdenum (Mo), and tungsten (W) can be used. As the gas containing halogen elements and transition metals, for example, TiCl4 gas, hafnium chloride (HfCl4) gas, zirconium chloride (ZrCl4) gas, tungsten hexafluoride (WF6) gas, tungsten hexachloride (WCl6) gas, molybdenum pentachloride (MoCl5) gas, molybdenum dioxide dichloride (MoO2Cl2) gas, molybdenum oxide tetrachloride (MoOCl4) gas, molybdenum hexafluoride (MoF6) gas, molybdenum dioxide difluoride (MoO2F2) gas, molybdenum oxide tetrafluoride (MoOF4) gas can be used. As the gas containing a halogen element and a transition metal, one or more of these can be used.

[0095] At this time, the source gas containing the halogen element is supplied to the wafer 200 on which hydrocarbon groups, amine groups, etc. derived from the gas containing the organic ligand are adsorbed, i.e., the wafer 200 whose surface is terminated with hydrocarbon groups or amine groups. Here, hydrocarbon groups and amine groups are adsorbed on the wafer 200 in the pre-process before the film formation process starts.

[0096] By supplying the raw material gas, the raw material gas is supplied to the chip 200 on which the hydrocarbon group, amine group, etc. as the organic ligand are exposed. As a result, the halogen element contained in the raw material gas reacts with the hydrocarbon group and amine group present on the chip 200, and the raw material element with a smaller molecular size than the raw material gas is adsorbed on the chip 200. Therefore, compared with the case of raw material gas adsorption, the steric hindrance becomes less. That is, the raw material element with a small molecular size is adsorbed on the chip 200 (the base film on the surface), which can increase the adsorption density of the raw material element on the chip 200 and form a raw material-containing layer with a high content of the raw material element. It should be noted that at this time, (CH3)Cl, (CH3)NCl, and (CH3)NHCl are generated as by-products. Most of the by-products are detached from the chip 200 and discharged. That is, the generation of reaction by-products such as hydrogen chloride (HCl) that hinder the adsorption of the raw material elements is suppressed.

[0097] Specifically, as described above, in this step, when TiCl4 gas is used as the raw material gas, Cl in the TiCl4 gas reacts with (CH3)- and (CH3)NH- on the wafer and is detached from the wafer 200 in the form of (CH3)Cl, (CH3)NCl, (CH3)NHCl, etc. x (x is less than 4) is adsorbed on the wafer 200. That is, TiCl4 has a smaller steric hindrance than TiCl4. x By being adsorbed on the wafer 200 , the adsorption density of the Ti element on the wafer 200 can be increased, and a Ti-containing layer having a high content of the Ti element can be formed.

[0098] In step 6, the APC valve 244 is adjusted so that the pressure in the processing chamber 201 is within a range of, for example, 1 to 3990 Pa. The supply flow rate of the raw material gas controlled by the MFC 241a is set to a flow rate within a range of, for example, 0.1 to 2.0 slm. The time for supplying the raw material gas to the wafer 200 is set to a time within a range of, for example, 0.01 to 30 seconds.

[0099] (Purge; Step 7)

[0100] After a predetermined time has passed since the supply of the raw material gas started, the valve 243a is closed to stop the supply of the raw material gas. At this time, the APC valve 244 of the exhaust pipe 231 is kept in an open state, and the processing chamber 201 is evacuated by the vacuum pump 246 to remove the residual gas from the wafer 200, and the unreacted raw material gas and reaction by-products remaining in the processing chamber 201 are discharged from the processing chamber 201. At this time, the valves 243e and 243f are kept in an open state to maintain the supply of the inert gas as the purge gas into the processing chamber 201. The seventh step can be performed under the same conditions as other purge steps.

[0101] (Reaction Gas Supply; Step 8)

[0102] After a predetermined time has passed since the start of the purge, the valve 243b is opened to allow the reaction gas to flow into the gas supply pipe 232b. The reaction gas is flow-regulated by the MFC 241b, supplied to the processing chamber 201 from the gas supply hole 250b of the nozzle 249b, and exhausted from the exhaust pipe 231. It should be noted that at this time, the valve 243f may also be opened at the same time to allow the inactive gas to flow into the gas supply pipe 232f. In addition, in order to prevent the reaction gas from invading the nozzle 249a, the valve 243e may also be opened to allow the inactive gas to flow into the gas supply pipe 232e.

[0103] At this time, the main gas flowing in the processing chamber 201 is the reaction gas, that is, the reaction gas is supplied to the wafer 200 .

[0104] As the reaction gas, for example, a H-containing gas containing hydrogen element (H) can be used. As the H-containing gas, for example, a gas containing H2 gas, ammonia (NH3) gas, hydrazine (N2H4) gas, diazine (N2H2) gas, H2O gas, H2O2 gas, a mixed gas of H2+O2, deuterium (D2) gas, deuterium ammonia (ND3) gas, monosilane (SiH4) gas, disilane (Si2H6) gas, trisilane (Si3H8) gas, monoborane (BH3) gas, diborane (B2H6) gas, B3H8 gas, phosphine (PH3) gas, etc. can be used. As the reaction gas, a gas obtained by activating one or more of them can be used.

[0105] By supplying the reaction gas, the reaction gas undergoes a substitution reaction with at least a portion of the first layer formed on the wafer 200, thereby forming the second layer. Specifically, when NH3 gas, for example, is used as the reaction gas, by supplying the NH3 gas, the NH3 gas undergoes a substitution reaction with at least a portion of the Ti-containing layer formed on the wafer 200. During the substitution reaction, Ti contained in the Ti-containing layer is bonded to N contained in the NH3 gas, thereby forming a TiN layer on the wafer 200. In addition, during the substitution reaction, the adsorption amount of the halogen element is reduced in the previous process, and the adsorption amount of Ti is increased in the film forming process, thereby suppressing the generation of reaction by-products such as HCl.

[0106] In step 8, the APC valve 244 is adjusted so that the pressure in the processing chamber 201 is within a range of, for example, 1 to 3990 Pa. The supply flow rate of the reaction gas controlled by the MFC 241b is set to a flow rate within a range of, for example, 0.1 to 30 slm. The time for supplying the reaction gas to the wafer 200 is set to a time within a range of, for example, 0.01 to 30 seconds.

[0107] (Purge; Step 9)

[0108] After a predetermined time has passed since the start of the supply of the reaction gas, the valve 243b is closed to stop the supply of the reaction gas. At this time, the APC valve 244 of the exhaust pipe 231 is kept in an open state, and the processing chamber 201 is evacuated by the vacuum pump 246 to remove the residual gas from the wafer 200, and the reaction gas and reaction byproducts that have not reacted or contributed to the formation of the second layer in the processing chamber 201 are exhausted from the processing chamber 201. At this time, the valves 243e and 243f are kept in an open state to maintain the supply of the inert gas as the purge gas into the processing chamber 201.

[0109] That is, the reaction gas remaining in the processing chamber 201 that has not reacted or has contributed to the formation of the second layer and the reaction by-products are exhausted from the processing chamber 201. The inert gas functions as a purge gas.

[0110] The ninth step can be performed under the same conditions as the other purge steps.

[0111] (Perform the specified number of times; step 10)

[0112] By performing the cycle of the sixth to ninth steps a predetermined number of times (n times, where n is an integer greater than or equal to 1 or 2), a predetermined film having a predetermined thickness is formed on the wafer 200. Here, as the predetermined film, a titanium nitride (TiN) film as a metal-containing film can be formed.

[0113] The processing in the above film forming step can be expressed as follows.

[0114] (raw material gas→purge→reactive gas→purge)×n

[0115] (n is an integer greater than 1 or 2)

[0116] (Perform the specified number of times; step 11)

[0117] After performing the above-mentioned step 10, the process returns to step 1. Then, by performing the cycle of the above-mentioned step 5 and the above-mentioned step 10 in sequence for a predetermined number of times (q times, q is an integer greater than or equal to 1 or 2), a predetermined film having a predetermined thickness is formed on the wafer 200. Here, as the predetermined film, a titanium nitride (TiN) film as a metal-containing film, for example, can be formed.

[0118] Therefore, the processing in the above substrate processing step can be expressed as follows.

[0119] [((promoter supply→purge 1)×p→purge 2→modifier→purge 3)×m→(raw material gas→purge 4→reactive gas→purge 5)×n]×q

[0120] (p, m, n, q are integers greater than or equal to 1 or 2, and may be different numbers, and may be adjusted appropriately.) It should be noted that purge 1, purge 2, and purge 3 may not be performed here.

[0121] (Post-purge and atmospheric pressure recovery)

[0122] An inert gas is supplied from each of the gas supply pipes 243e and 243f into the processing chamber 201, and the gas is exhausted from the exhaust pipe 231. The inert gas acts as a purge gas, and the processing chamber 201 is purged with the inert gas, and the residual gas and reaction by-products in the processing chamber 201 are removed from the processing chamber 201 (post-purge). Then, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure recovery).

[0123] (Wafer removal)

[0124] Then, the sealing cover 219 is lowered by the wafer boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the wafer boat 217 (wafer boat unloading). Then, the processed wafer 200 is taken out of the wafer boat 217 (wafer taking out).

[0125] Here, the film formed on the wafer 200 using the substrate processing sequence without performing the previous step sometimes grows in an island shape and does not become a continuous film. That is, the adsorption of the raw material elements on the wafer 200 is insufficient, and the coverage rate is poor. In contrast, for the film formed on the wafer 200 using the above-mentioned substrate processing sequence, the crystal grains are small and formed continuously at a high density, and the coverage rate becomes high.

[0126] That is, by performing the pre-process before the film forming process, adsorption of the raw material elements onto the wafer 200 can be promoted, the adsorption density of the raw material elements can be increased, and a film with a high content of the raw material elements can be formed.

[0127] That is, by supplying an accelerator and a modifier before forming a film, adsorption of the raw material elements onto the wafer surface can be promoted, and a thin film with a high coverage can be formed.

[0128] (3) Effects of this method

[0129] According to this aspect, one or more of the following effects can be obtained.

[0130] (a) The characteristics of a film formed on a substrate can be improved.

[0131] (b) The film formed on the substrate can be grown continuously. The term "continuous" here means that the crystals of the film material are connected and the intervals between the crystals are small.

[0132] (c) It can increase the adsorption density of raw material elements and improve the coverage rate.

[0133] (d) In the film forming step, the generation of reaction by-products that inhibit the adsorption of raw material elements such as HCl can be suppressed.

[0134] (4) Other methods

[0135] One embodiment of the present invention has been specifically described above, but the present invention is not limited to the above embodiment, and various modifications can be made without departing from the gist of the present invention.

[0136] (Variant 1)

[0137] In this modification, an organic gas is used as the accelerator used in the above-mentioned pre-process. As the organic gas, for example, a gas containing alkanes is used. As the gas containing alkanes, a gas composed of C n H 2n+2 The constituent gas includes, for example, methane (CH4), ethane (C2H6), propane (C3H8), etc. As the accelerator, one or more of these can be used.

[0138] By supplying an organic gas as a promoter, hydrocarbon groups are adsorbed on the wafer 200. That is, by supplying an organic gas, the surface of the wafer 200 is terminated with CH-. Thereby, the adsorption of the modifier is promoted. It should be noted that when an organic gas is used, the possibility of excessively denaturing the state of the film exposed on the surface of the wafer 200 can be reduced. For example, when the surface of the wafer 200 contains a film of a metal element, when the oxidizing gas of the present invention is used, an oxide film containing the metal element is sometimes formed. By forming an oxide film, there is a possibility of affecting the characteristics of the semiconductor device. On the other hand, when an organic gas is used, such a problem can be prevented from occurring. It should be noted that when the film exposed on the surface of the wafer 200 contains oxygen, the possibility of such a problem occurring is low even if the oxidizing gas of the present invention is used.

[0139] In this case, the same Figure 4 The same effect is achieved in the order of substrate processing shown.

[0140] (Variant 2)

[0141] In this modification, the above-mentioned film forming process is performed as follows. "+" means a time point when there is simultaneous flow. "()" means that it can be omitted.

[0142] (raw material gas → raw material gas + reducing gas → (reducing gas) → purge → reaction gas → purge) × n

[0143] (n is an integer greater than 1 or 2)

[0144] In this case, the same Figure 4 The same effect is achieved in the order of substrate processing shown.

[0145] Specifically, for example, TiCl 4 gas can be used as the raw material gas, NH 3 gas can be used as the reaction gas, and SiH 4 gas can be used as the reducing gas, and it can also be appropriately applied to the case of forming a TiN film or the like by the above sequence.

[0146] (Variant 3)

[0147] In the above-mentioned method, the case where the above-mentioned substrate processing sequence is continuously (in-situ) performed in the same processing chamber (processing container) is described. The present invention is not limited to the above-mentioned method. For example, Figure 5 As shown, the process may be performed using a cluster type substrate processing apparatus 10 having a plurality of processing furnaces 202a to 202d, for example, a plurality of processing chambers 201a to 201d are connected to a vacuum transfer chamber 103 provided with a substrate transfer device 112. That is, at least any one of the processes and any other one of the processes in the above-mentioned substrate processing sequence may be performed in different processing chambers (processing containers) (ex-situ).

[0148] In this modification, the controller 121 performs, for example, the above-mentioned pre-process and the above-mentioned film forming process in different processing chambers of different processing furnaces. In this case, the controller 121, which is a host computer or a group management control device, controls the controller 121A that performs the pre-process in the processing furnace for the pre-process and the controller 121B that performs the film forming process in the processing furnace for the film forming process. That is, the substrate processing device 10 performs the pre-process of supplying the accelerator and the modifier, and the film forming process of supplying the raw material gas and the reaction gas in different processing chambers. In any case, the same effect as the above-mentioned method can be obtained. It should be noted that, when these processes are performed in situ, the contamination of the substrate, the change of the surface state of the substrate, etc. that may occur due to the substrate being carried out of the processing chamber or carried in from the processing chamber during the processing can be suppressed. In addition, when these processes are performed in situ, the transfer time during the processing can be shortened. On the other hand, when these processes are performed ex-situ, each process can be performed in parallel in different processing chambers, and the productivity can be improved accordingly.

[0149] When these substrate processing apparatuses are used, each process can be performed under the same process steps and process conditions as those of the above-mentioned embodiment and the modified example, and the same effects as those of the above-mentioned embodiment and the modified example can be obtained.

[0150] In the above-mentioned embodiment, an example in which the accelerator is supplied in time division as a pre-process is described, but the present invention is not limited to this, and the embodiment is also applicable to a case in which the accelerator is supplied continuously.

[0151] In the above embodiment, the case where the inert gas is continuously supplied during the substrate processing step is described as an example, but the present invention is not limited to this, and the inert gas may be supplied only during the purge step.

[0152] In addition, in the above-mentioned method, an example of forming a film using a batch-type substrate processing device that processes a plurality of substrates at a time is described. The present invention is not limited to the above-mentioned method, and for example, it can also be suitably applied to the case where a film is formed using a single-wafer type substrate processing device that processes one or several substrates at a time. In addition, in the above-mentioned method, an example of forming a film using a substrate processing device having a hot-wall type processing furnace is described. The present invention is not limited to the above-mentioned method, and it can also be suitably applied to the case where a film is formed using a substrate processing device having a cold-wall type processing furnace.

[0153] The above-mentioned aspects and modifications may be used in combination as appropriate. The processing steps and processing conditions in this case may be the same as those of the above-mentioned aspects and modifications, for example.

[0154] As mentioned above, although the aspect and the modification of this invention were demonstrated concretely, the aspect and the modification of this invention are not limited to the above-mentioned aspect and the modification, Various changes can be made within the range which does not deviate from the summary.

Claims

1. A substrate processing method, comprising: (a) a step of supplying a non-reducing accelerator to a substrate, wherein: The promoter promotes the adsorption of the modifier comprising an organic ligand; (b) supplying the modifying agent to the substrate; and (c) After performing (a) and (b), a step of forming a film on the substrate.

2. The substrate processing method according to claim 1, wherein: The modifier does not contain any metal element.

3. The substrate processing method according to claim 1, wherein: The modifier contains a metal element.

4. The substrate processing method according to claim 1, wherein: The modifier comprises a hydrocarbon group.

5. The substrate processing method according to claim 1, wherein: The modifier comprises an amine.

6. The substrate processing method according to claim 1, wherein: The accelerator is oxidizing.

7. The substrate processing method according to claim 6, wherein: The promoter is a gas that does not contain hydrogen element.

8. The substrate processing method according to claim 1, wherein: The accelerator is an organic gas.

9. The substrate processing method according to claim 8, wherein: The promoter is a gas containing an alkane.

10. The substrate processing method according to claim 1, wherein: (c) A gas containing a halogen element is used.

11. The substrate processing method according to claim 10, wherein: The gas containing the halogen element contains a metal element.

12. The substrate processing method according to claim 1, wherein: (c) A gas containing a metal element and a halogen element is used, and the reformer does not contain a metal element.

13. The substrate processing method according to claim 1, wherein: Repeat (a) multiple times.

14. The substrate processing method according to claim 1, comprising (d) a step of removing the accelerator. Repeat (a) and (d) a specified number of times.

15. The substrate processing method according to claim 1 or 13, wherein: (e) Repeat (a) and (b) a prescribed number of times.

16. The substrate processing method according to claim 15, wherein: Repeat (e) and (c) a prescribed number of times.

17. The substrate processing method according to claim 10, wherein: In (c), a reaction gas containing hydrogen element is supplied.

18. A method for manufacturing a semiconductor device, comprising: (a) a step of supplying a non-reducing accelerator to a substrate, wherein: The promoter promotes the adsorption of the modifier comprising an organic ligand; (b) supplying the modifying agent to the substrate; and (c) After performing (a) and (b), a step of forming a film on the substrate.

19. A computer-readable recording medium having a program recorded thereon for causing a substrate processing apparatus to execute the following steps using a computer: (a) supplying a non-reducing accelerator to the substrate, wherein: The promoter promotes the adsorption of the modifier comprising an organic ligand; (b) a step of supplying the modifying agent to the substrate; and (c) After performing (a) and (b), a step of forming a film on the substrate.

20. A substrate processing apparatus comprising: a first gas supply system capable of supplying a non-reducing promoter containing an organic ligand and promoting adsorption of a modifier to the substrate; a second gas supply system capable of supplying the modifier to the substrate; and A control unit configured to control the first gas supply system and the second gas supply system to: (a) supplying the accelerator to the substrate; (b) supplying the modifying agent to the substrate; and (c) After performing (a) and (b), a process of forming a film on the substrate.

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