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

Abstract

A substrate processing method according to the present invention comprises: (a) a step for supplying an adsorption inhibition gas to a substrate; (b) a step for supplying a starting material gas to the substrate; (c) a step for supplying a reaction gas to the substrate; and (d) a step for forming a film of the elements contained in the starting material gas on the substrate by performing the steps (a), (b) and (c) a predetermined number of times in a state where the amount of the starting material gas supplied in the step (b) to be exposed to the substrate is set higher than the amount of the adsorption inhibition gas supplied in the step (a) to be exposed to the substrate.

Description

Technical Field

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

Background Art

[0002] As one step in the manufacturing process of a semiconductor device, a substrate processing step may be performed in which a raw material gas or a reaction gas is supplied to a substrate to form a film on the substrate (see, for example, Japanese Patent Application Laid-Open No. 2014-135475).

Summary of the Invention

Problems to be Solved by the Invention

[0003] The present disclosure provides a technique capable of improving the characteristics of a film formed on a substrate.

Means for Solving the Problems

[0004] According to one aspect of the present disclosure, a) a step of supplying an adsorption-inhibiting gas to a substrate; b) a step of supplying a raw material gas to the substrate; c) a step of supplying a reaction gas to the substrate; d) a step of performing a), b), and c) a predetermined number of times in a state where the exposure amount of the raw material gas supplied in b) to the substrate is made larger than the exposure amount of the adsorption-inhibiting gas supplied in a) to the substrate, and forming a film of an element contained in the raw material gas on the substrate, is provided.

Effects of the Invention

[0005] According to the present disclosure, it becomes possible to provide a technique capable of improving the characteristics of a film formed on a substrate.

Brief Description of the Drawings

[0006] [Figure 1] It is a longitudinal sectional view showing an outline of a vertical processing furnace of a substrate processing apparatus in an embodiment of the present disclosure. [Figure 2]Figure 1 is a schematic cross-sectional view along line AA. [Figure 3] This is a schematic diagram of the controller of a substrate processing apparatus in one embodiment of the present disclosure, and shows the controller's control system in block diagram form. [Figure 4] This figure shows an example of a substrate processing step in one embodiment of the present disclosure. [Figure 5] This graph conceptually shows the relationship between the amount of exposure of the wafer to an adsorption-inhibiting gas and the amount of improvement in step coverage in one embodiment of the present disclosure. [Figure 6] In one embodiment of this disclosure, this is a graph conceptually showing the relationship between the amount of exposure of the wafer to the adsorption-inhibiting gas and the amount of adsorption of the adsorption-inhibiting gas molecules onto the wafer. [Figure 7] In one embodiment of this disclosure, this is a graph conceptually showing the relationship between the amount of exposure of the wafer to the raw material gas and the amount of adsorption of raw material gas molecules onto the wafer. [Figure 8] In one embodiment of this disclosure, this is a graph conceptually showing the relationship between the amount of reaction gas exposure to the wafer and the amount of reaction gas molecules adsorbed onto the wafer. [Figure 9] This is a longitudinal cross-sectional view showing a schematic of a vertical processing furnace of a substrate processing apparatus in a modified embodiment of one embodiment of the present disclosure. [Modes for carrying out the invention]

[0007] The following explanation will be given with reference to Figures 1-9. Please note that the drawings used in the following explanation are all schematic, and the dimensional relationships and ratios of each element shown in the drawings do not necessarily correspond to reality. Furthermore, the dimensional relationships and ratios of each element do not necessarily correspond between multiple drawings.

[0008] (1) Configuration of substrate processing apparatus The substrate processing apparatus 10 includes a processing furnace 202 equipped with a heater 207 as a heating means (heating mechanism, heating system). The heater 207 is cylindrical in shape and is mounted vertically by being supported by a heater base (not shown) which serves as a holding plate.

[0009] Inside the heater 207, an outer tube 203, which constitutes a reaction tube (reaction vessel, processing vessel), is arranged concentrically with the heater 207. The outer tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and is formed in a cylindrical shape with a closed upper end and an open lower end. Below the outer tube 203, a manifold (inlet flange) 209 is arranged concentrically with the outer tube 203. The manifold 209 is made of a metal such as stainless steel (SUS), and is formed in a cylindrical shape with open upper and lower ends. An O-ring 220a is provided between the upper end of the manifold 209 and the outer tube 203 as a sealing member. The manifold 209 is supported by the heater base, so that the outer tube 203 is installed vertically.

[0010] An inner tube 204, which constitutes the reaction vessel, is arranged inside the outer tube 203. The inner tube 204 is made of a heat-resistant material such as quartz or SiC, and is formed in a cylindrical shape with a closed upper end and an open lower end. The processing vessel (reaction vessel) is mainly composed of the outer tube 203, the inner tube 204, and the manifold 209. A processing chamber 201 is formed in the hollow cylindrical part of the processing vessel (inside the inner tube 204).

[0011] The processing chamber 201 is configured to accommodate wafers 200 as substrates, arranged in multiple vertical layers in a horizontal position using boats 217 as supports.

[0012] Within the processing chamber 201, nozzles 410, 420, and 430 are provided so as to penetrate the side wall of the manifold 209 and the inner tube 204. Gas supply pipes 310, 320, and 330 are connected to the nozzles 410, 420, and 430, respectively. However, the processing furnace 202 of this embodiment is not limited to the above configuration.

[0013] Gas supply pipes 310, 320, and 330 are each equipped with flow controllers (flow control units), namely mass flow controllers (MFCs) 312, 322, and 332, respectively, from upstream to downstream. Gas supply pipes 310, 320, and 330 are also equipped with on-off valves, namely valves 314, 324, and 334, respectively. Downstream from the valves 314, 324, and 334 on gas supply pipes 310, 320, and 330 are connected to gas supply pipes 510, 520, and 530, respectively, which supply inert gas. Gas supply pipes 510, 520, and 530 are each equipped with flow controllers (flow control units), namely MFCs 512, 522, and 532, and on-off valves, namely valves 514, 524, and 534, respectively, from upstream to downstream.

[0014] Nozzles 410, 420, and 430 are connected to the ends of the gas supply pipes 310, 320, and 330, respectively. The nozzles 410, 420, and 430 are configured as L-shaped nozzles, with their horizontal portions penetrating the side wall of the manifold 209 and the inner tube 204. The vertical portions of the nozzles 410, 420, and 430 are located inside a channel-shaped (groove-shaped) spare chamber 201a that protrudes radially outward from the inner tube 204 and extends vertically. Furthermore, the vertical portions of the nozzles 410, 420, and 430 are located within the spare chamber 201a, extending upward (upward in the direction of wafer 200 arrangement) along the inner wall of the inner tube 204.

[0015] The nozzles 410, 420, 430 are provided so as to extend from the lower region to the upper region of the processing chamber 201. At positions facing the wafer 200 in the nozzles 410, 420, 430, a plurality of gas supply holes 410a, 420a, 430a are provided respectively. Thereby, the processing gas is supplied to the wafer 200 from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 respectively. A plurality of these gas supply holes 410a, 420a, 430a are provided from the lower part to the upper part of the inner tube 204. Further, the gas supply holes 410a, 420a, 430a each have the same opening area. Furthermore, the gas supply holes 410a, 420a, 430a are arranged at the same pitch. However, the gas supply holes 410a, 420a, 430a are not limited to the above-described form. For example, the opening area of the gas supply holes 410a, 420a, 430a may be gradually increased from the lower part to the upper part of the inner tube 204. Thereby, it becomes possible to make the flow rate of the gas supplied from the gas supply holes 410a, 420a, 430a to the wafer 200 more uniform.

[0016] A plurality of gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 are provided extending from the lower part to the upper part of the boat 217. Therefore, the processing gas supplied into the processing chamber 201 from the gas supply holes 410a, 420a, 430a of the nozzles 410, 420, 430 is supplied to the entire area of the wafer 200 accommodated from the lower part to the upper part of the boat 217. The nozzles 410, 420, 430 only need to be provided so as to extend from the lower region to the upper region of the processing chamber 201, but it is preferable that they are provided so as to extend up to near the ceiling of the boat 217.

[0017] From the gas supply pipe 310, as the processing gas, the source gas is supplied into the processing chamber 201 via the MFC 312, the valve 314, and the nozzle 410.

[0018] From the gas supply pipe 320, as the processing gas, the reaction gas is supplied into the processing chamber 201 via the MFC 322, the valve 324, and the nozzle 420.

[0019] From the gas supply pipe 330, as a processing gas, an adsorption inhibition gas that inhibits the adsorption of Group 14 elements, different from the reaction gas, is supplied into the processing chamber 201 through the MFC 332, the valve 334, and the nozzle 430. In the present disclosure, the adsorption inhibition gas is also referred to as an adsorption suppression gas, a reaction inhibition gas, or a surface modification gas.

[0020] From the gas supply pipes 510, 520, 530, as an inert gas, for example, nitrogen (N2) gas is supplied into the processing chamber 201 through the MFCs 512, 522, 532, the valves 514, 524, 534, and the nozzles 410, 420, 430, respectively. Hereinafter, an example using N2 gas as the inert gas will be described, but as the inert gas, in addition to N2 gas, for example, noble gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas may be used.

[0021] When flowing the raw material gas through the gas supply pipe 310, mainly, the gas supply pipe 310, the MFC 312, and the valve 314 constitute the raw material gas supply system (the first gas supply system), but the nozzle 410 may also be considered to be included in the raw material gas supply system. Also, when flowing the reaction gas through the gas supply pipe 320, mainly, the gas supply pipe 320, the MFC 322, and the valve 324 constitute the reaction gas supply system (the third gas supply system), but the nozzle 420 may also be considered to be included in the reaction gas supply system. Also, when flowing the adsorption inhibition gas through the gas supply pipe 330, mainly, the gas supply pipe 330, the MFC 332, and the valve 334 constitute the adsorption inhibition gas supply system (the second gas supply system), but the nozzle 430 may also be considered to be included in the adsorption inhibition gas supply system. Also, the raw material gas supply system, the reaction gas supply system, and the adsorption inhibition gas supply system can also be referred to as the processing gas supply system. Also, the nozzles 410, 420, 430 may be considered to be included in the processing gas supply system. Also, mainly, the gas supply pipes 510, 520, 530, the MFCs 512, 522, 532, and the valves 514, 524, 534 constitute the inert gas supply system.

[0022] Furthermore, the gas supply pipe 310 may also be provided with a storage section 701 for storing the processed gas, and a valve 702 on the downstream side (processing chamber 201) of the storage section 701.

[0023] In this embodiment, gas is transported into the inner tube 204 via nozzles 410, 420, and 430 located in a preliminary chamber 201a within a vertically elongated, annular space defined by the inner wall of the inner tube 204 and the edges of multiple wafers 200. Gas is then ejected into the inner tube 204 from multiple gas supply holes 410a, 420a, and 430a located on the nozzles 410, 420, and 430 facing the wafers 200. More specifically, raw material gas and the like are ejected from the gas supply hole 410a of nozzle 410, the gas supply hole 420a of nozzle 420, and the gas supply hole 430a of nozzle 430 in a direction parallel to the surface of the wafers 200.

[0024] The exhaust port (exhaust vent) 204a is a through-hole formed in the side wall of the inner tube 204, opposite the nozzles 410, 420, and 430, and is, for example, a slit-shaped through-hole that is elongated vertically. The gas supplied into the processing chamber 201 from the gas supply holes 410a, 420a, and 430a of the nozzles 410, 420, and 430, and flowing over the surface of the wafer 200, flows through the exhaust port 204a into the gap (inside the exhaust passage 206) formed between the inner tube 204 and the outer tube 203. The gas that flows into the exhaust passage 206 then flows into the exhaust pipe 231 and is discharged outside the processing furnace 202.

[0025] The exhaust port 204a is located opposite to the multiple wafers 200. The gas supplied from the gas supply ports 410a, 420a, and 430a to the vicinity of the wafers 200 in the processing chamber 201 flows horizontally and then flows into the exhaust passage 206 through the exhaust port 204a. The exhaust port 204a is not limited to being a slit-shaped through-hole, but may also be composed of multiple holes.

[0026] An exhaust port 231a provided in the manifold 209 is connected to an exhaust pipe 231 that exhausts the atmosphere inside the processing chamber 201. Connected to the exhaust pipe 231, in order from the upstream side, are a pressure sensor 245 which acts as a pressure detector (pressure detection unit) for detecting the pressure inside the processing chamber 201, an APC (Auto Pressure Controller) valve 243, and a vacuum pump 246 which acts as a vacuum evacuation device. The APC valve 243 can be opened and closed while the vacuum pump 246 is operating to perform vacuum evacuation and stop vacuum evacuation inside the processing chamber 201. Furthermore, the APC valve 243 can adjust the pressure inside the processing chamber 201 by adjusting the valve opening while the vacuum pump 246 is operating. The exhaust system mainly consists of the exhaust port 204a, the exhaust passage 206, the exhaust pipe 231, the APC valve 243, and the pressure sensor 245. The vacuum pump 246 may also be considered as part of the exhaust system.

[0027] Below the manifold 209, a seal cap 219 is provided as a furnace opening cover capable of hermetically closing the lower end opening of the manifold 209. The seal cap 219 is configured to abut the lower end of the manifold 209 from the vertically downward side. The seal cap 219 is made of a metal such as SUS and is formed in a disc shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a sealing member that abuts the lower end of the manifold 209. On the opposite side of the processing chamber 201 in the seal cap 219, a rotating mechanism 267 is installed to rotate a boat 217 that houses the wafers 200. The rotation shaft 255 of the rotating mechanism 267 passes through the seal cap 219 and is connected to the boat 217. The rotating mechanism 267 is configured to rotate the wafers 200 by rotating the boat 217. The seal cap 219 is configured to be raised and lowered vertically by a boat elevator 115, which is installed vertically outside the outer tube 203 as a lifting mechanism. The boat elevator 115 is configured to allow the boat 217 to be moved in and out of the processing chamber 201 by raising and lowering the seal cap 219. The boat elevator 115 is configured as a transport device (transport mechanism, transport system) for transporting the boat 217 and the wafers 200 contained in the boat 217 to the inside and outside of the processing chamber 201.

[0028] The boat 217 is configured to hold multiple wafers 200, for example 25 to 200 wafers 200, in a horizontal position, with their centers aligned and spaced apart vertically. The boat 217 is made of a heat-resistant material such as quartz or SiC. A dummy substrate 218, also made of a heat-resistant material such as quartz or SiC, is supported in multiple stages in a horizontal position at the bottom of the boat 217. This configuration makes it difficult for heat from the heater 207 to be transferred to the seal cap 219. However, this embodiment is not limited to the above configuration. For example, instead of providing a dummy substrate 218 at the bottom of the boat 217, a heat-insulating cylinder, which is a cylindrical member made of a heat-resistant material such as quartz or SiC, may be provided.

[0029] As shown in Figure 2, a temperature sensor 263 is installed inside the inner tube 204 as a temperature detector. The substrate processing apparatus 10 is configured to adjust the amount of current supplied to the heater 207 based on the temperature information detected by the temperature sensor 263 so that the temperature inside the processing chamber 201 reaches a desired temperature distribution. The temperature sensor 263 is configured in an L-shape, similar to the nozzles 410, 420, and 430, and is installed along the inner wall of the inner tube 204.

[0030] As shown in Figure 3, the controller 121, which is the control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, storage device 121c, and I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are connected to the CPU 121a via an internal bus so as to be able to exchange data. An input / output device 122, configured as, for example, a touch panel, is connected to the controller 121.

[0031] The storage device 121c is composed of, for example, flash memory or an HDD (Hard Disk Drive). The storage device 121c contains, in a readable format, a control program that controls the operation of the substrate processing device, and a process recipe that describes the procedures and conditions for the semiconductor device manufacturing method (substrate processing method) described later. The process recipe is a combination of steps that cause the controller 121 to execute each process (each step) in the semiconductor device manufacturing method (substrate processing method) described later, thereby obtaining a predetermined result, and functions as a program. Hereinafter, this process recipe and control program will be collectively referred to simply as a program. In this specification, the term "program" may include only the process recipe, only the control program, or a combination of the process recipe and the control program. The RAM 121b is configured as a memory area (work area) where programs and data read by the CPU 121a are temporarily held.

[0032] I / O port 121d is connected to the aforementioned MFCs 312, 322, 332, 512, 522, 532, valves 314, 324, 334, 514, 524, 534, 702, pressure sensor 245, APC valve 243, vacuum pump 246, heater 207, temperature sensor 263, rotating mechanism 267, and boat elevator 115, etc.

[0033] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read process recipes and other data from the storage device 121c in response to input of operation commands from the input / output device 122. The CPU 121a is configured to control the flow rate adjustment operations of various gases by MFCs 312, 322, 332, 512, 522, and 532, the opening and closing operations of valves 314, 324, 334, 514, 524, 534, and 702, the gas storage operation in the storage section 701 by valve 702, the opening and closing operations of APC valve 243, the pressure adjustment operation based on the pressure sensor 245 by APC valve 243, the temperature adjustment operation of heater 207 based on temperature sensor 263, the starting and stopping of vacuum pump 246, the rotation and rotation speed adjustment operations of boat 217 by rotating mechanism 267, the raising and lowering operation of boat 217 by boat elevator 115, and the storage operation of wafers 200 in boat 217, etc., in accordance with the contents of the read process recipe.

[0034] The controller 121 can be configured by installing the above-mentioned program stored in an external storage device (for example, magnetic tape, magnetic disks such as flexible disks or hard disks, optical disks such as CDs or DVDs, magneto-optical disks such as MOs, or semiconductor memory such as USB memory or memory cards) 123 into a computer. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to simply as recording media. In this specification, a recording media may include only the storage device 121c, only the external storage device 123, or both the storage device 121c and the external storage device 123. The program may be provided to the computer using communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0035] (2) Substrate processing process As one step in the manufacturing process of a semiconductor device, an example of a process for forming a silicon nitride (SiN) film, for example, used as a charge trap film for 3D NAND, on a wafer 200 will be explained with reference to Figure 4. The process of forming the silicon nitride film is carried out using the processing furnace 202 of the substrate processing apparatus 10 described above. In this embodiment, an example will be described in which a silicon substrate (silicon wafer) having recesses such as trenches and holes on its surface is used as the wafer 200. In the following description, the operation of each part constituting the substrate processing apparatus 10 is configured to be controllable by the controller 121.

[0036] In the substrate processing process (semiconductor manufacturing process) according to this embodiment, a) A step of supplying an adsorption inhibiting gas into a processing chamber 201 containing a wafer 200 having recesses on its surface, b) A step of supplying a raw material gas into a processing chamber 201 containing a wafer 200, c) A step of supplying a reaction gas into a processing chamber 201 containing a wafer 200, Steps a), b), and c) are performed a predetermined number of times, under the condition that the amount of raw material gas supplied in d) and b) exposed to the wafer 200 is greater than the amount of adsorption inhibiting gas supplied in a) exposed to the wafer 200, thereby forming a film of elements contained in the raw material gas on the wafer 200.

[0037] In this disclosure, the above-described film deposition sequence may also be shown as follows for convenience. The same notation will be used in the description of other embodiments.

[0038] (Adsorption inhibiting gas → Source gas → Reaction gas) × n Here, n is a natural number (1 or an integer greater than or equal to 2).

[0039] In this specification, the term "wafer" may mean either "the wafer itself" or "a laminate of a wafer and a predetermined layer or film formed on its surface." In this specification, the term "surface of a wafer" may mean either "the surface of the wafer itself" or "the surface of a predetermined layer or film formed on the wafer." In this specification, the term "substrate" has the same meaning as the term "wafer."

[0040] (Wafer delivery) Once multiple wafers 200 are loaded into the boat 217 (wafer charging), the boat 217 supporting the multiple wafers 200 is lifted by the boat elevator 115 and transported into the processing chamber 201 (boat loading), as shown in Figure 1. The boat 217 supporting the multiple wafers 200 is then placed in the processing container. In this state, the seal cap 219 closes the lower end opening of the outer tube 203 via the O-ring 220.

[0041] (Pressure adjustment and temperature adjustment) The processing chamber 201, i.e., the space where the wafer 200 is located, is evacuated by a vacuum pump 246 to a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by a pressure sensor 245. Based on the pressure information measured by the pressure sensor 245, the APC valve 243 is feedback controlled (pressure adjustment). The vacuum pump 246 is kept running continuously at least until the processing of the wafer 200 is completed. The processing chamber 201 is also heated by a heater 207 to a desired temperature. At this time, the amount of power supplied to the heater 207 is feedback controlled based on the temperature information detected by the temperature sensor 263 to ensure a desired temperature distribution inside the processing chamber 201 (temperature adjustment). Heating of the processing chamber 201 by the heater 207 is continued at least until the processing of the wafer 200 is completed.

[0042] [Step 1] (Supplying process of adsorption-inhibiting gas) The controller 121 opens valve 334, allowing adsorption-inhibiting gas to flow into the gas supply pipe 330. After the flow rate of the adsorption-inhibiting gas is adjusted by MFC 332, it is supplied into the processing chamber 201 from the gas supply hole 430a of the nozzle 430. The adsorption-inhibiting gas supplied into the processing chamber 201 is exhausted through the exhaust pipe 231. At this time, the adsorption-inhibiting gas is supplied to the wafer 200. Alternatively, the controller 121 may open valve 534 and allow an inert gas such as N2 gas to flow into the gas supply pipe 530. The N2 gas that has flowed through the gas supply pipe 530 is after its flow rate is adjusted by MFC 532 and supplied into the processing chamber 201 together with the adsorption-inhibiting gas. The N2 gas supplied into the processing chamber 201 is exhausted through the exhaust pipe 231. At this time, in order to prevent adsorption-inhibiting gas from entering the nozzles 410 and 420, the controller 121 opens valves 512 and 524 and flows N2 gas into the gas supply pipes 510 and 520. The N2 gas is supplied into the processing chamber 201 via the gas supply pipes 310 and 320 and the nozzles 410 and 420, and exhausted from the exhaust pipe 231.

[0043] At this time, the controller 121 adjusts the APC valve 243 to set the pressure in the processing chamber 201 to a pressure within the range of 1 to 3990 Pa, for example, 1000 Pa. The supply flow rate of the adsorption inhibiting gas controlled by the MFC 332 is set to a flow rate within the range of 0.005 to 5.0 slm. Here, the controller 121 adjusts the pressure in the processing chamber 201, the supply flow rate of the adsorption inhibiting gas into the processing chamber 201, and the supply time so that the amount of exposure of the wafer 200 to the adsorption inhibiting gas becomes a first exposure amount. In this disclosure, the first exposure amount is determined, for example, by the product of the partial pressure of the adsorption inhibiting gas in the processing chamber 201 and the supply time of the adsorption inhibiting gas into the processing chamber 201 (partial pressure × time). Furthermore, the first exposure amount is less than the second exposure amount described later. The N2 gas supply flow rate controlled by MFC512,522,532 is set to a flow rate within the range of, for example, 0.1 to 5.0 slm, respectively, in order to suppress the entry of gas containing Group 15 elements into each nozzle 410,420,430. At this time, the temperature of the heater 207 is set to a temperature such that the temperature of the wafer 200 is within the range of, for example, 250 to 800°C, preferably 600 to 700°C. In this disclosure, numerical range notations such as "1 to 3990 Pa" mean that the lower limit and upper limit are included in that range. Therefore, for example, "1 to 3990 Pa" means "1 Pa or more and 3990 Pa or less". The same applies to other numerical ranges. The first exposure amount may be the product of the supply flow rate and supply time of the adsorption-inhibiting gas into the processing chamber 201 (supply flow rate × supply time), the product of the total pressure in the processing chamber 201 and the supply time of the adsorption-inhibiting gas into the processing chamber 201 (total pressure × supply time), or the product of the partial pressure (total pressure) in the processing chamber 201 and the supply flow rate and supply time of the adsorption-inhibiting gas into the processing chamber 201 (partial pressure (total pressure) × supply flow rate × supply time). The supply flow rate of the adsorption-inhibiting gas into the processing chamber 201 is affected by the volume of the processing container and the pattern of the recesses formed on the wafer 200. Therefore, it is preferable that the first exposure amount be the product of the partial pressure in the processing chamber 201 and the supply time of the adsorption-inhibiting gas into the processing chamber 201.

[0044] Preferably, the amount of adsorption-inhibiting gas exposed to the wafer 200 (first exposure amount, adsorption amount) is set to the amount at which the improvement in step coverage of the film formed on the wafer 200 saturates, as shown in the graph in Figure 5.

[0045] Furthermore, preferably, as shown in the graph in Figure 6, the amount of adsorption-inhibiting gas exposed to the wafer 200 (first exposure amount, adsorption amount) is the amount at which molecules of the adsorption-inhibiting gas saturately adsorb to the wafer 200. Even more preferably, the amount of adsorption-inhibiting gas exposed to the wafer 200 (first exposure amount) is the amount at which molecules of the adsorption-inhibiting gas saturately adsorb to the opening side (upper side of the recess) of the recess formed on the surface of the wafer 200. In other words, preferably, the amount of adsorption-inhibiting gas exposed to the wafer 200 is the amount at which the adsorption of molecules of the adsorption-inhibiting gas saturates on the wafer 200. Even more preferably, the amount of adsorption-inhibiting gas exposed to the wafer 200 is the amount at which the adsorption of molecules of the adsorption-inhibiting gas saturates to the opening side (upper side of the recess) of the recess formed on the surface of the wafer 200.

[0046] In this disclosure, saturation does not necessarily mean that all adsorbable sites on the wafer 200 are filled; it is sufficient if it is substantially saturated. In other words, for the purpose of improving productivity, it is acceptable even if it is not completely saturated, or to put it another way, even if the reaction has not completely converged. Furthermore, in combinations of gas species and film species where the reaction amount characteristics with respect to gas supply time have a saturating curve in a region where this curve is greater than a certain supply time, the use of a state that is not completely saturated on the saturating curve may also be referred to as saturated adsorption in this disclosure. At least one effect of this disclosure can be obtained with a single supply time on the saturating curve. When the supply time is set in a region of supply time where such a saturating curve can be obtained, it can also be called supply utilizing the saturating adsorption characteristics.

[0047] The adsorption inhibiting gas supplied to the wafer 200 is, for example, a halogen-containing gas. A halogen-containing gas is a gas containing at least one element from Group 17. Examples of such gases include hydrogen halides such as hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), and hydrogen iodide (HI). The adsorption inhibiting gas may also be a gas composed of halogen elements, such as fluorine (F2), chlorine (Cl2), bromine (Br2), and iodine (I2). Alternatively, the adsorption inhibiting gas may be a gas containing two types of halogen elements, such as nitrogen trifluoride (NF3) and chlorine trifluoride (ClF3). Preferably, a highly polar gas is used as the adsorption inhibiting gas. Such a highly polar gas is, for example, a hydrogen halide gas, specifically HCl gas. Molecules of such highly polar gases are easily adsorbed onto the wafer 200. Furthermore, highly polarized gases can suppress the adsorption of decomposition products generated by the decomposition of the source gas, in addition to the adsorption of the source gas itself, as described later. If adsorption to wafer 200 is not a consideration, a gas such as Cl2 can be used as the adsorption inhibiting gas. Compared to hydrogen halides, Cl2 has less polarity, but its molecular size is larger than that of hydrogen halides. Due to its large molecular size, Cl2 has the effect of hindering the adsorption of source gas molecules and decomposition products generated by the decomposition of the source gas. In other words, the adsorption inhibitor acts as a steric hindrance.

[0048] By supplying such a gas to the wafer 200, adsorption inhibitors are formed on the surface of the wafer 200. These adsorption inhibitors consist of molecules containing halogen elements or the halogen elements themselves.

[0049] Furthermore, by exposing (supplying) the wafer 200 with the adsorption inhibiting gas at a first exposure level, molecules of the adsorption inhibiting gas, or a portion of the adsorption inhibiting gas molecules, can be adsorbed onto the upper side of the recesses formed on the surface of the wafer 200.

[0050] Furthermore, the adsorption inhibiting gas is not limited to inorganic substances as described above, but may also be an organic adsorption inhibiting gas. An organic adsorption inhibiting gas is, for example, a gas containing an alkyl group (alkyl ligand). An alkyl group is, for example, a methyl group. A methyl group is electrically negative and repels negatively charged raw material molecules, making it difficult for it to bond with those raw material molecules. For example, a methyl group (Me-) and a halogen (Cl-) contained in the raw material molecule are both negatively charged and therefore difficult to bond with. Here, Me means methyl. In other words, by adsorbing a substance containing an alkyl group onto a specific location on the wafer 200, it is possible to suppress the adsorption of the raw material gas supplied thereafter onto that specific location on the wafer 200. Examples of substances containing alkyl groups include hexamethyldisilazane (abbreviation: HMDSN), dimethylaminotrimethylsilane (abbreviation: DMATMS), trimethylsilanol (abbreviation: TMS), and triethylsilanol (abbreviation: TES).

[0051] [Step 2] (Removal of residual gases) After a predetermined time has elapsed since the start of the adsorption-inhibiting gas supply, for example, 1 to 600 seconds, the controller 121 closes the valve 334 of the gas supply pipe 330 to stop the supply of the adsorption-inhibiting gas. At this time, the controller 121 keeps the APC valve 243 of the exhaust pipe 231 open and uses the vacuum pump 246 to evacuate the inside of the processing chamber 201, removing any unreacted or adsorption-inhibiting gas that has contributed to the formation of adsorption inhibitors remaining in the processing chamber 201. In other words, the controller 121 evacuates the atmosphere inside the processing chamber 201. By lowering the pressure inside the processing chamber 201, gas containing element 15 remaining in the gas supply pipe 330 and nozzle 430 can be evacuated. By evacuating the adsorption-inhibiting gas remaining in the gas supply pipe 330 and nozzle 430, it is possible to suppress the supply of the adsorption-inhibiting gas remaining in the gas supply pipe 330 and nozzle 430 into the processing chamber 201 during the film formation process. In this case, the controller 121 may keep valves 514, 524, and 534 open and maintain the supply of N2 gas into the processing chamber 201. The N2 gas acts as a gas intrusion suppression gas to each nozzle 410, 420, and 430, as well as a purge gas. When N2 gas is supplied into the processing chamber 201 as a purge gas, the effect of removing gas containing unreacted or adsorption-inhibiting gas that has contributed to the formation of adsorption inhibitors remaining in the processing chamber 201 can be enhanced.

[0052] [Third step] (Raw material gas supply process) Next, the controller 121 opens valve 314, allowing the raw material gas to flow into the gas supply pipe 310. After the flow rate of the raw material gas is adjusted by MFC 312, it is supplied into the processing chamber 201 from the gas supply hole 410a of the nozzle 410. The raw material gas supplied into the processing chamber 201 is exhausted through the exhaust pipe 231. This supplies the raw material gas to the wafer 200. At this time, the controller 121 opens valve 514, allowing an inert gas such as N2 gas to flow into the gas supply pipe 510. After the flow rate of the N2 gas flowing through the gas supply pipe 510 is adjusted by MFC 512, it is supplied into the processing chamber 201 together with the raw material gas. The N2 gas supplied into the processing chamber 201 is exhausted through the exhaust pipe 231. At this time, in order to prevent the raw material gas from entering the nozzles 420 and 430, the controller 121 opens valves 524 and 534, allowing N2 gas to flow into the gas supply pipes 520 and 530. N2 gas is supplied into the processing chamber 201 via gas supply pipes 320, 330 and nozzles 420, 430, and then exhausted through exhaust pipe 231.

[0053] At this time, the controller 121 adjusts the APC valve 243 to set the pressure in the processing chamber 201 to a pressure within the range of 1 to 3990 Pa, for example, 500 Pa. The supply flow rate of the raw material gas controlled by the MFC 312 is set to a flow rate within the range of 1 to 2000 sccm, preferably 10 to 1000 sccm. Here, the supply conditions of the raw material gas are set so that the amount of exposure of the wafer 200 to the raw material gas is greater than the first exposure amount, which is a second exposure amount. In this disclosure, the second exposure amount is, for example, the product of the partial pressure of the raw material gas in the processing chamber 201 and the supply time of the raw material gas into the processing chamber 201 (partial pressure × time). The supply flow rates of the N2 gas controlled by the MFCs 512, 522, and 532 are set to flow rates within the range of 0.1 to 5.0 slm, respectively. At this time, the temperature of the heater 207 is set to such a temperature that the temperature of the wafer 200 is, for example, within the range of 250 to 800°C, preferably 600 to 700°C. The second exposure amount in this disclosure may also be the product of the supply flow rate and supply time of the raw material gas into the processing chamber 201 (supply flow rate × supply time), the product of the total pressure in the processing chamber 201 and the supply time of the raw material gas into the processing chamber 201 (total pressure × supply time), or the product of the partial pressure (total pressure) in the processing chamber 201 and the supply flow rate and supply time of the raw material gas into the processing chamber 201 (partial pressure (total pressure) × supply flow rate × supply time). The supply flow rate of the raw material gas into the processing chamber 201 is affected by the volume of the processing container, the pattern of the recesses formed on the wafer 200, etc. Therefore, it is preferable that the second exposure amount be the product of the partial pressure in the processing chamber 201 and the supply time of the raw material gas into the processing chamber 201.

[0054] Furthermore, the amount of gas exposure to the wafer 200 in this disclosure can also be rephrased as the amount of gas molecules adsorbed onto the surface of the wafer 200. As mentioned above, this amount of adsorption can be adjusted, for example, by the product of the partial pressure of the gas (adsorption inhibiting gas or raw material gas) in the processing chamber 201 and the supply time of the gas (adsorption inhibiting gas or raw material gas) into the processing chamber 201 (partial pressure × time).

[0055] To make the second exposure amount (adsorption amount) in this disclosure greater than the first exposure amount (adsorption amount), this can be adjusted by making at least one of the partial pressure, total pressure, supply flow rate, and supply time related to the second exposure amount greater than at least one of the partial pressure, total pressure, supply flow rate, and time related to the first exposure amount.

[0056] Here, the second exposure amount (adsorption amount) of the raw material gas is preferably set to an amount at which the adsorption of raw material gas molecules onto the wafer 200 does not saturate, as shown in the graph in Figure 7. In other words, the second exposure amount (adsorption amount) of the raw material gas is preferably set to an amount at which the molecules of the raw material gas do not saturate adsorb onto the wafer 200.

[0057] Alternatively, the raw material gas may be stored in a storage unit 701 and supplied from the storage unit 701 into the processing chamber 201. When the raw material gas stored in the storage unit 701 is supplied into the processing chamber 201, the supply time of the raw material gas into the processing chamber 201 may be shorter than the supply time of the adsorption-inhibiting gas into the processing chamber 201. In this case, for example, the exposure amounts of the raw material gas and the adsorption-inhibiting gas (first exposure amount and second exposure amount) are adjusted so that the product of the partial pressure (total pressure) of the raw material gas in the processing chamber 201 and the supply time of the raw material gas into the processing chamber 201 is greater than the product of the partial pressure (total pressure) of the adsorption-inhibiting gas in the processing chamber 201 and the supply time of the adsorption-inhibiting gas into the processing chamber 201. In addition, in the raw material gas supply process (third process), the supply of raw material gas into the processing chamber 201 may be performed not only once but multiple times. When supplying raw material gas to the processing chamber 201 multiple times, the supply of raw material gas to the processing chamber 201 shall be stopped between a predetermined number of times and the next time. Furthermore, when supplying raw material gas to the processing chamber 201 multiple times, at least once, the raw material gas stored in the storage unit 701 may be supplied to the processing chamber 201. For example, when supplying raw material gas to the processing chamber 201 two or more times, the first time, the raw material gas stored in the storage unit 701 is supplied to the processing chamber 201, and the second time, raw material gas is supplied to the processing chamber 201 without storing any raw material gas in the storage unit 701. Between the first and second times, the supply of raw material gas to the processing chamber 201 shall be stopped. Additionally, the processing chamber 201 may be evacuated (pressurized) in conjunction with the cessation of the supply of raw material gas to the processing chamber 201, or an inert gas may be supplied to the processing chamber 201 in conjunction with the evacuation. The supply and cessation of raw material gas into the processing chamber 201 are controlled, for example, by opening and closing valve 702.

[0058] As the raw material gas supplied to the wafer 200, for example, a silane-based gas containing Si as the main element constituting the film formed on the wafer 200 can be used. As the silane-based gas, for example, a gas containing Si and halogens, i.e., halosilane gas, can be used. Halogens include chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. As the halosilane gas, for example, chlorosilane gas containing Si and Cl can be used.

[0059] As raw material gases, for example, chlorosilane gases such as monochlorosilane (SiH3Cl, abbreviated as MCS) gas, dichlorosilane (SiH2Cl2, abbreviated as DCS) gas, trichlorosilane (SiHCl3, abbreviated as TCS) gas, tetrachlorosilane (SiCl4, abbreviated as STC) gas, hexachlorodisilane (Si2Cl6, abbreviated as HCDS) gas, and octachlorotrisilane (Si3Cl8, abbreviated as OCTS) gas can be used. One or more of these can be used as raw material gases.

[0060] In addition to chlorosilane gas, other raw material gases that can be used include fluorosilane gases such as tetrafluorosilane (SiF4) gas and difluorosilane (SiH2F2) gas, bromosilane gases such as tetrabromosilane (SiBr4) gas and dibromosilane (SiH2Br2) gas, and iodosilane gases such as tetraiodosilane (SiI4) gas and diiodosilane (SiH2I2) gas. One or more of these can be used as raw material gases.

[0061] In addition to the above, other gases containing Si and amino groups, such as aminosilane gas, can also be used as raw material gases. An amino group is a monovalent functional group obtained by removing hydrogen (H) from ammonia, a primary amine, or a secondary amine, and can be represented as -NH2, -NHR, or -NR2. Note that R represents an alkyl group, and the two R's in -NR2 may be the same or different.

[0062] For example, aminosilane gases such as tetrakis(dimethylamino)silane (Si[N(CH3)2]4, abbreviated as 4DMAS) gas, tris(dimethylamino)silane (Si[N(CH3)2]3H, abbreviated as 3DMAS) gas, bis(diethylamino)silane (Si[N(C2H5)2]2H2, abbreviated as BDEAS) gas, bis(tert-butylamino)silane (SiH2[NH(C4H9)]2, abbreviated as BTBAS) gas, and (diisopropylamino)silane (SiH3[N(C3H7)2], abbreviated as DIPAS) gas can also be used as raw material gases. One or more of these can be used as raw material gases.

[0063] This disclosure describes an example in which HCDS gas is used as the raw material gas. When HCDS gas is used as the raw material gas, a silicon (Si)-containing layer containing chlorine (Cl) of a predetermined thickness can be formed as the first layer on the outermost surface of the wafer 200. The Si-containing layer containing Cl can be formed by physical or chemical adsorption of molecules of the raw material gas onto the outermost surface of the wafer 200, physical or chemical adsorption of molecules of substances obtained by the decomposition of at least some of the molecules of the raw material gas (also called decomposition products), or deposition of Si by thermal decomposition of the raw material gas. In this disclosure, decomposition products are also referred to as ligands of the raw material gas or parts of the ligands of the raw material gas. When HCDS is used as the raw material, for example, the decomposition product is SiClx, where x is 2, 3, or 4. The Si-containing layer containing Cl may be an adsorption layer (physical adsorption layer or chemical adsorption layer) of molecules of chlorosilane gas or molecules of substances obtained by the decomposition of some of the chlorosilane gas, or it may be a deposited layer of Si containing Cl. When the above-mentioned chemical adsorption layer or the above-mentioned deposition layer is formed on the outermost surface of the wafer 200, Si contained in the chlorosilane gas will be adsorbed on the outermost surface of the wafer 200. In this disclosure, the Si-containing layer containing Cl is also simply referred to as the Si-containing layer.

[0064] Furthermore, in this disclosure, an adsorption inhibiting gas is supplied before the HCDS gas is supplied, and adsorption inhibitors are formed on the surface of the wafer 200 by the adsorption inhibiting gas. When HCl gas is used as the adsorption inhibiting gas, adsorption inhibitors such as HCl and Cl, which is a part of HCl, are formed on the surface of the wafer 200. Such adsorption inhibitors suppress the adsorption of HCDS gas molecules and SiClx. In other words, the presence of adsorption inhibitors can suppress the adsorption of some of the ligands of the source gas. Depending on the composition of the molecules (atoms) that make up the adsorption inhibitors, it is possible to suppress the adsorption of a specific number of SiClx molecules.

[0065] [Step 4] (Removal of residual gases) After a predetermined time has elapsed since the start of raw material gas supply, for example, 1 to 60 seconds, the controller 121 closes the valve 314 of the gas supply pipe 310 to stop the supply of raw material gas. In other words, the time for which raw material gas is supplied to the wafer 200 is, for example, within the range of 1 to 60 seconds. At this time, the controller 121 leaves the APC valve 243 of the exhaust pipe 231 open and uses the vacuum pump 246 to evacuate the processing chamber 201, removing any unreacted or residual raw material gas that has contributed to layer formation from the processing chamber 201. That is, the controller 121 exhausts the atmosphere inside the processing chamber 201. At this time, the controller 121 may leave valves 514, 524, and 534 open and maintain the supply of N2 gas into the processing chamber 201. The N2 gas acts as a gas that suppresses gas entry into each nozzle 410, 420, and 430, as well as a purge gas. When N2 gas is supplied as a purge gas, the effect of removing unreacted or layer-forming raw material gas remaining in the processing chamber 201 from the processing chamber 201 can be enhanced.

[0066] [Step 5] (Reaction gas supply) After removing residual gas from the processing chamber 201, the controller 121 opens valve 324 and allows reaction gas to flow into the gas supply pipe 320. The reaction gas is flow-rate regulated by MFC 322 and then supplied into the processing chamber 201 from the gas supply hole 420a of nozzle 420. The reaction gas supplied into the processing chamber 201 is exhausted through exhaust pipe 231. At this time, the reaction gas is supplied to the wafer 200. Also at this time, the controller 121 keeps valves 514, 524, and 534 open to maintain the supply of N2 gas into the gas supply pipes 510, 520, and 530. The N2 gas flowing through the gas supply pipes 510, 520, and 530 is flow-rate regulated by MFCs 512, 522, and 532, respectively. N2 gas flowing through gas supply pipe 520 is supplied to the processing chamber 201 along with the reaction gas via gas supply pipe 320 and nozzle 420, and then exhausted through exhaust pipe 231. Similarly, N2 gas flowing through gas supply pipe 530 is supplied to the processing chamber 201 via gas supply pipe 330 and nozzle 430, and then exhausted through exhaust pipe 231. N2 gas flowing through gas supply pipe 510 is supplied to the processing chamber 201 via gas supply pipe 310 and nozzle 410, and then exhausted through exhaust pipe 231. This suppresses the entry of reaction gas into nozzle 410.

[0067] At this time, the controller 121 adjusts the APC valve 243 to set the pressure in the processing chamber 201 to a pressure within the range of 1 to 13300 Pa, for example, 5000 Pa. The supply flow rate of the reaction gas controlled by the MFC 322 is set to a flow rate within the range of 1 to 50 slm, preferably 15 to 40 slm. The supply flow rates of the N2 gas controlled by the MFCs 512, 522, and 532 are set to flow rates within the range of 0.1 to 5.0 slm, respectively.

[0068] The amount of reaction gas exposure (adsorption amount) to the wafer 200 is preferably the amount at which the adsorption of reaction gas molecules to the wafer 200 becomes saturated, as shown in the graph in Figure 8. In other words, the amount of reaction gas exposure (adsorption amount) to the wafer 200 is preferably the amount at which the reaction gas molecules become saturated and adsorbed on the wafer 200.

[0069] As the reaction gas supplied to the wafer 200, for example, a nitrogen (N) and hydrogen (H) containing gas, which is a nitriding gas (nitriding agent), can be used. The N and H containing gas is both an N-containing gas and an H-containing gas. It is preferable that the N and H containing gas has an NH bond.

[0070] In this disclosure, the term "agent" includes at least one of gaseous substances and liquid substances. Liquid substances include mist-like substances. That is, film-forming agents, modifiers, and etching agents may contain gaseous substances, liquid substances such as mist-like substances, or both.

[0071] Examples of reaction gases that can be used include hydrogen nitride-based gases such as ammonia (NH3), diazene (N2H2), hydrazine (N2H4), and N3H8. One or more of these gases can be used as the reaction gas.

[0072] In addition to these, other reaction gases such as nitrogen (N), carbon (C), and hydrogen (H) gases can also be used. Examples of N, C, and H-containing gases include amine gases and organic hydrazine gases. An N, C, and H-containing gas is also an N-containing gas, a C-containing gas, an H-containing gas, and an N and C-containing gas.

[0073] Examples of reaction gases that can be used include ethylamine gases such as monoethylamine (C2H5NH2, abbreviated as MEA) gas, diethylamine ((C2H5)2NH, abbreviated as DEA) gas, and triethylamine ((C2H5)3N, abbreviated as TEA) gas; methylamine gases such as monomethylamine (CH3NH2, abbreviated as MMA) gas, dimethylamine ((CH3)2NH, abbreviated as DMA) gas, and trimethylamine ((CH3)3N, abbreviated as TMA) gas; and organic hydrazine gases such as monomethylhydrazine ((CH3)HN2H2, abbreviated as MMH) gas, dimethylhydrazine ((CH3)2N2H2, abbreviated as DMH) gas, and trimethylhydrazine ((CH3)2N2(CH3)H, abbreviated as TMH) gas. One or more of these can be used as the reaction gas. These gases are also called amine gases.

[0074] [Step 6] (Removal of residual gases) After a predetermined time has elapsed since the start of the reaction gas supply, for example, 1 to 1200 seconds, the controller 121 closes the valve 324 of the gas supply pipe 320 to stop the supply of reaction gas. Then, using the same processing procedure as in the second step described above, the controller 121 removes any unreacted reaction gas or reaction by-products that have contributed to the formation of the layer remaining in the processing chamber 201. In other words, the controller 121 exhausts the atmosphere inside the processing chamber 201.

[0075] (Performed the prescribed number of times) By performing the above-described steps 1 to 6 in sequence in a cycle at least once (a predetermined number of times (n times, where n is an integer of 1 or 2 or more)), a film of elements contained in the raw material gas of a predetermined thickness is formed on the wafer 200. For example, a silicon nitride film (SiN film) can be formed on the wafer 200. It is preferable to repeat the above cycle multiple times.

[0076] (After-purge and return to atmospheric pressure) The controller 121 supplies N2 gas into the processing chamber 201 from gas supply pipes 510, 520, and 530, respectively. The N2 gas supplied into the processing chamber 201 is exhausted through the exhaust pipe 231. The N2 gas acts as a purge gas. This purges the processing chamber 201 with an inert gas, removing any remaining gases and reaction by-products from the processing chamber 201 (after-purge). Subsequently, the atmosphere inside the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure inside the processing chamber 201 is returned to atmospheric pressure (atmospheric pressure return).

[0077] (Wafer removal) Subsequently, the seal cap 219 is lowered by the boat elevator 115, opening the lower end of the outer tube 203. Then, the processed wafer 200, supported by the boat 217, is unloaded from the lower end of the outer tube 203 to the outside of the outer tube 203 (boat unloading). After that, the processed wafer 200 is removed from the boat 217 (wafer discharge).

[0078] (3) Effects of this embodiment According to this embodiment, one or more of the following effects can be obtained.

[0079] (a) By supplying an adsorption-inhibiting gas to the wafer 200, the adsorption of a large amount of raw material gas to specific locations on the wafer 200 can be suppressed. Therefore, the thickness of the film in specific locations on the wafer 200 can be suppressed, and the film thickness in other locations can be increased. In addition, molecules of the raw material gas adsorbed to specific locations on the wafer 200 can be made to reach other locations. In other words, the amount of raw material gas consumed at specific locations on the wafer 200 can be reduced, and the amount of raw material gas consumed at other locations on the wafer 200 can be increased. Here, specific locations are, for example, the following locations: locations close to the nozzle of the wafer 200, or, if a recess is formed in the wafer 200, the upper side of the recess, etc. If the specific location is close to the nozzle of the wafer 200, the uniformity of the film thickness in the plane of the wafer 200 as a film characteristic can be improved. If the specific location is the upper side of a recess, the amount of raw material gas adsorbed (consumed) on the upper side of the recess can be reduced, and the amount of raw material gas adsorbed (consumed) on the bottom side of the recess can be increased. This improves the uniformity of the film thickness in the depth direction of the recess, specifically the film formed on the walls and bottom of the recess. In other words, it improves the step coverage as a characteristic of the film.

[0080] (b) By making the exposure (adsorption) of the raw material gas greater than the exposure (adsorption) of the adsorption-inhibiting gas (in other words, making the exposure (adsorption) of the adsorption-inhibiting gas less than the exposure (adsorption) of the raw material gas), molecules of the adsorption-inhibiting gas can be adsorbed mainly at specific locations on the wafer 200. As a result, the amount of raw material gas adsorbed at specific locations on the wafer 200 can be reduced compared to the amount of raw material gas adsorbed at other locations on the wafer 200. In addition, the amount of raw material gas adsorbed at other locations on the wafer 200 can be increased. As a result, the difference in film thickness between specific locations on the wafer 200 and other locations on the wafer 200 can be reduced. That is, film thickness uniformity can be improved. If recesses are formed on the wafer 200, film thickness uniformity within the recesses can be improved. In other words, step coverage can be improved.

[0081] (c) By increasing the exposure amount of the adsorption inhibiting gas, the uniformity of the film thickness of the wafer 200 can be improved. In particular, if recesses are formed in the wafer 200, the step coverage of the film formed in the recesses can be improved. On the other hand, as the exposure amount of the adsorption inhibiting gas is increased, for example, as shown in the graph in Figure 5, the improvement in step coverage stops increasing beyond a certain value. In other words, the improvement in step coverage saturates. Therefore, it is preferable that the exposure amount of the adsorption inhibiting gas be set to the amount at which the improvement in step coverage saturates.

[0082] The saturation of such step coverage improvement is thought to be due to the saturation of the amount of adsorption inhibiting gas adsorbed at a specific location on the wafer 200. Therefore, it is preferable that the exposure amount of the adsorption inhibiting gas be set to the amount at which molecules of the adsorption inhibiting gas saturately adsorb onto the wafer 200, as shown in the graph in Figure 6. By setting the exposure amount of the adsorption inhibiting gas to the amount at which molecules of the adsorption inhibiting gas saturately adsorb onto the wafer 200, it is possible to obtain the maximum amount of step coverage improvement. The amount at which molecules of the adsorption inhibiting gas saturately adsorb onto the wafer 200 is defined as the amount at which molecules of the adsorption inhibiting gas saturately adsorb onto a specific location on the wafer 200. If the specific location is a recess, it should be at least the amount at which the amount of adsorption inhibiting gas molecules adsorbed on the upper side of the recess saturates. This reduces the amount of raw material gas adsorbed on the upper side of the recess and increases the amount of raw material gas adsorbed on the lower side of the recess, thereby improving the uniformity of the film thickness within the recess.

[0083] (d) Even when a gas that decomposes in the gas phase is used as the raw material gas, the uniformity of the film formed on the wafer 200, in particular, the step coverage of recesses can be improved. Examples of gases that decompose in the gas phase are chlorosilane-based gases, specifically HCDS gas. When HCDS is used, the decomposition of HCDS produces decomposition products such as SiCl2 and SiCl4. Of these, SiCl2 undergoes a CVD reaction. The occurrence of the CVD reaction prevents the relationship between the supply time of the raw material gas to the wafer 200 and the increase in the film thickness of the wafer 200 (film thickness per cycle) from becoming saturated. That is, an unsaturated characteristic is obtained. The unsaturated characteristic means that even if the supply time of the raw material gas to the wafer 200 increases, the film thickness of the wafer 200 (film thickness per cycle) does not converge to a predetermined value. In this case, for example, as shown in the graph in Figure 7, the amount of raw material gas exposure to the wafer 200 is such that the amount of raw material gas molecules adsorbed on the wafer 200 does not become saturated. When a film is formed on wafer 200 under conditions that yield this unsaturated characteristic, the film thickness at specific locations on wafer 200 increases, potentially degrading the uniformity of the film thickness of wafer 200. The step coverage of the film formed in recesses may also deteriorate. According to the technology of this disclosure, by supplying an adsorption-inhibiting gas to wafer 200, the adsorption of intermediates that produce unsaturated characteristics, such as SiCl2, onto wafer 200 can be suppressed. As a result, the uniformity of the film thickness of wafer 200 can be improved. Furthermore, when a wafer 200 having recesses is processed, the step coverage of the film formed in the recesses can be improved. Among these decomposition products, the amount of SiCl2 produced is proportional to the supply time of HCDS gas to wafer 200. That is, as the supply time of HCDS gas to wafer 200 increases, the amount of SiCl2 produced increases. This increase in SiCl2 production is due to the increased residence time of HCDS molecules in the processing chamber 201 as the HCDS supply time to wafer 200 increases. In other words, it is thought that an increase in the residence time of HCDS molecules in processing chamber 201 means that the HCDS molecules are heated for a longer period of time in processing chamber 201, and thus the number of molecules that are thermally decomposed increases.To reduce the amount of SiCl2 generated and the amount of SiCl2 adsorbed onto the wafer 200, it is preferable to reduce the supply time of HCDS gas to the wafer 200. To reduce the supply time of HCDS gas to the wafer 200, it is preferable to supply the HCDS gas to the wafer 200 instantaneously (also called flash supply) using the storage unit 701.

[0084] (e) As shown in the graph in Figure 8, the uniformity of the film thickness of the wafer 200 can be improved by setting the amount of reaction gas exposure to the wafer 200 to the amount at which reaction gas molecules are saturated and adsorbed onto the wafer 200. Furthermore, the step coverage of the film formed in the recesses of the wafer 200 can be improved. In addition, a sufficient amount of reaction gas molecules can be supplied to the raw material gas molecules whose adsorption to the wafer 200 is suppressed by the adsorption inhibiting gas. Therefore, the effect of improving the uniformity of the film thickness of the wafer 200 obtained by supplying the adsorption inhibiting gas to the wafer 200 can be improved. On the other hand, if the amount of reaction gas exposure to the wafer 200 is insufficient, the raw material gas molecules adsorbed on the wafer 200 will remain on the wafer 200 without reacting with the reaction gas. For example, if the raw material gas molecules remaining on the wafer 200 are HCDS itself, there is a possibility that the decomposition product, SiCl2, will be generated. If SiCl2 is generated, as mentioned above, it will be a factor in the deterioration of the uniformity of the film thickness of the wafer 200. Also, there is a possibility that the raw material gas molecules remaining on the wafer 200 will detach from the wafer 200 as is. Furthermore, the molecules of the raw material gas remaining on the wafer 200 may suppress the adsorption of the adsorption-inhibiting gas onto the wafer 200, or inhibit the adsorption of the raw material gas onto the wafer 200, in the next cycle.

[0085] (f) By reducing the exposure of the wafer 200 to the adsorption-inhibiting gas to less than the exposure of the wafer 200 to the raw material gas, the step coverage of the film formed in the recesses of the wafer 200 can be made 70% or more.

[0086] (g) By reducing the exposure of the wafer 200 to the adsorption-inhibiting gas to less than the exposure of the wafer 200 to the raw material gas, the difference in step coverage in the depth direction of the film formed in the recesses of the wafer 200 can be reduced to within 20%.

[0087] (h) By using an inorganic adsorption inhibiting gas (for example, a gas containing halogen elements) as the adsorption inhibiting gas, the increase in the amount of impurities in the film formed on the wafer 200 due to the adsorption inhibiting gas can be reduced. Here, impurities are elements other than the main elements that make up the film formed on the wafer 200. On the other hand, the molecular size of organic adsorption inhibiting gases is larger than that of inorganic adsorption inhibiting gases. Therefore, when an organic adsorption inhibiting gas is used as the adsorption inhibiting gas, the effect of the adsorption inhibiting gas acting as steric hindrance to inhibit the adsorption of the raw material gas onto the wafer 200 is greater than when an inorganic adsorption inhibiting gas is used.

[0088] It is preferable to use a gas of a highly polarized substance as the adsorption inhibiting gas. In this disclosure, polarity refers to molecular polarity. By using a gas of a highly polarized substance as the adsorption inhibiting gas, the amount of adsorption of the adsorption inhibiting gas onto the wafer 200 can be increased. When a gas of a less polarized substance is used as the adsorption inhibiting gas, it may not be possible to obtain a sufficient amount of adsorption of the adsorption inhibiting gas onto the wafer 200, but the molecular size of a less polarized substance may be large. When the molecular size of a less polarized substance is large, the molecule itself acts as a steric hindrance, thus reducing the amount of adsorption of the raw material gas onto the wafer 200. Here, a substance containing a highly polarized halogen element is, for example, a substance containing a halogen element and other elements. These other elements are, for example, elements other than those in Group 17 of the periodic table, preferably Group 1 elements. Specifically, these include HCl, HBr, HI, and HF. A substance containing a less polarized halogen element is, for example, a substance composed of halogen elements. Specifically, these include Cl2, F2, Br2, and I2. Furthermore, highly polarized gases (specifically HCl gas) have a tendency to adsorb easily onto NH-terminants. Therefore, it is preferable to supply a gas containing NH- groups to the wafer 200 before supplying the adsorption-inhibiting gas to the wafer 200. Gases containing NH- groups include, for example, inorganic NH-group-containing gases and organic NH-group-containing gases. Specific examples of inorganic NH-group-containing gases include ammonia (NH3) gas and hydrazine (N2H4) gas. Examples of organic NH-group-containing gases include gases containing amine groups. Gases containing amine groups include the amine-based gases mentioned above. When using the above-mentioned NH-group-containing gas as the reaction gas, NH-terminants are formed on the surface of the wafer 200 by the reaction gas supplied to the wafer 200 during the first cycle of film formation on the wafer 200. Since the adsorption-inhibiting gas for the second cycle is supplied to the wafer 200 with these NH-terminants formed, it becomes possible to maintain or improve the adsorption characteristics of the adsorption-inhibiting gas to the wafer 200 from the second cycle onward. Alternatively, before supplying the first adsorption-inhibiting gas to the wafer 200, a gas containing NH- groups may be supplied to the wafer 200 to form NH-terminants on the surface of the wafer 200.In this case, it is preferable to set the supply conditions for the NH-containing gas so that the gas containing the NH- group is supplied to a specific location on the wafer 200. This is because if the NH-terminants are formed on the entire surface of the wafer 200, particularly to the bottom of a recess in the wafer 200, the adsorption-inhibiting gas may be adsorbed on the bottom of the recess, making it difficult to obtain the effects described above.

[0089] <Other aspects of this disclosure> The aspects of this disclosure have been specifically described above. However, this disclosure is not limited to the aspects described above and can be modified in various ways without departing from its essence.

[0090] In the above embodiment, as shown in Figure 1, the raw material gas is supplied into the processing chamber 201 from the nozzle 410 of one gas supply pipe 310. However, as shown in the modified example in Figure 9, the raw material gas may be supplied into the processing chamber 201 from the nozzles 410 of two gas supply pipes 310. In Figure 9, elements that are substantially the same as those described in Figure 1 are denoted by the same reference numerals.

[0091] In the modified example shown in Figure 9, compared to the above embodiment where the raw material gas is supplied into the processing chamber 201 from the nozzle 410 of a single gas supply pipe 310, the amount of raw material gas supplied from the nozzle 410 of each gas supply pipe 310 into the processing chamber 201 can be reduced. As a result, the rise in internal pressure within each nozzle 410 is suppressed, and therefore the temperature rise of the raw material gas is suppressed. Consequently, the decomposition of the raw material gas (e.g., HCDS) associated with the temperature rise is suppressed. Therefore, the generation of SiCl2, a decomposition product of the raw material gas (HCDS), can be suppressed. Furthermore, the same effects as in the above embodiment can be obtained in this modified example.

[0092] Furthermore, the film deposition sequence of the above embodiment is as follows, as described above. (Adsorption inhibiting gas → Source gas → Reaction gas) × n However, the film deposition sequence of the above embodiment can be modified as appropriate. For example, as shown in the following modified examples (S1 to S5), a reaction gas may be supplied to the wafer 200, followed by an adsorption-inhibiting gas. In other words, the wafer 200 may be post-treated with an adsorption-inhibiting gas. The adsorption-inhibiting gas is an example of a halogen-containing gas. S1: (Source gas → Reaction gas → P + Adsorption inhibiting gas → V) × n S2: (Source gas → Reaction gas → (P + adsorption inhibiting gas → V → adsorption inhibiting gas) × c) × n S3: (Source gas → Reaction gas → P → V + Adsorption inhibiting gas) × n S4: (Source gas → Reaction gas → (P / V) × c → Adsorption inhibiting gas → (P / V) × d) × n S5: (Source gas → Reaction gas → Adsorption inhibiting gas → (P / V) × c) × n However, n, c, and d are natural numbers (1 or integers greater than or equal to 2). Also, n, c, and d may be the same natural number or different natural numbers. Furthermore, the exposure control described in the above embodiment does not need to be applied in these film deposition sequences. Also, the adsorption inhibiting gas does not need to be supplied before the raw material gas in these film deposition sequences. Even without doing these things, at least one of the effects described later can be achieved.

[0093] Note that "P" stands for purge. Specifically, the controller 121 opens valves 512, 524, and 534 and supplies an inert gas such as N2 gas into the processing chamber 201 via gas supply pipes 310, 320, and 330, and nozzles 410, 420, and 430. The inert gas such as N2 gas supplied into the processing chamber 201 is exhausted through the exhaust pipe 231. Furthermore, "P + adsorption inhibiting gas" means that the supply of adsorption inhibiting gas into the processing chamber 201 (first step) and purging are performed simultaneously.

[0094] "V" represents the residual gas removal (second step) mentioned above. "V + adsorption inhibiting gas" means that the residual gas removal (second step) and the supply of the adsorption inhibiting gas into the processing chamber 201 are performed simultaneously. "(P / V) × c" means that purging and residual gas removal (second step) are repeated c times. After the supply of the "raw material gas" and the supply of the "reaction gas," residual gas removal (fourth step and sixth step) may be performed, respectively.

[0095] If reaction gas is adsorbed at a specific location on wafer 200, in the next cycle, the raw material gas will be adsorbed onto the reaction gas adsorbed at that location on wafer 200, making CVD-like reactions more likely to occur. As a result, the film thickness at that specific location on wafer 200 may increase, potentially worsening the step coverage of wafer 200. This problem is particularly likely to occur when multiple molecules of the reaction gas are adsorbed at that specific location on wafer 200.

[0096] As a countermeasure, in this modified example, as in the film deposition sequence (S1-S5) described above, after supplying the reaction gas into the processing chamber 201, an adsorption-inhibiting gas is supplied into the processing chamber 201. This causes the reaction gas adsorbed at specific locations on the wafer 200 to react with the adsorption-inhibiting gas, generating a reaction product. In other words, the reaction gas adsorbed at specific locations on the wafer 200 can be detached from those locations as a reaction product. Therefore, the amount of reaction gas adsorbed at specific locations on the wafer 200 is reduced, and CVD-like reactions (gas-phase reactions) on the wafer 200 can be suppressed. As a result, deterioration of the step coverage of the wafer 200 can be suppressed. That is, step coverage can be improved. In addition, since the adsorption-inhibiting gas is adsorbed at the specific locations on the wafer 200 from which the reaction gas has desorbed, the adsorption of the raw material gas to those specific locations is suppressed in the next cycle. Therefore, the step coverage of the wafer 200 can be further improved.

[0097] Furthermore, by simultaneously supplying an adsorption-inhibiting gas into the processing chamber 201 and purging (P), as described in the aforementioned film deposition sequence (S1, S2), the effect of removing residual reaction gases and gases containing the generated reaction products from the processing chamber 201 can be enhanced.

[0098] Furthermore, in the aforementioned film deposition sequence (S1, S2), after supplying an adsorption-inhibiting gas into the processing chamber 201, residual gas removal (second step) is performed to remove the adsorption-inhibiting gas and other substances from the processing chamber 201. This makes it possible to remove the reaction gases remaining in the processing chamber 201 and the gases containing the generated reaction products from the processing chamber 201. Subsequently, as in the aforementioned film deposition sequence (S2), the adsorption-inhibiting gas may be supplied into the processing chamber 201. As a result, the adsorption-inhibiting gas is adsorbed at specific locations on the wafer 200 from which the reaction gas has desorbed, further suppressing the adsorption of the raw material gas at those specific locations in the next cycle. In other words, it is also possible to obtain the effect of filling the sites on the wafer 200 where molecules of the raw material gas would adsorb with the adsorption-inhibiting gas.

[0099] Furthermore, as in the aforementioned film deposition sequence (S2), by repeating (P + adsorption inhibiting gas → V → adsorption inhibiting gas) a predetermined number of times (c times, where c is 1 or an integer of 2 or more), the amount of reaction gas adsorbed at specific locations on the wafer 200 can be further reduced, and the adsorption inhibiting gas can be further adsorbed at specific locations on the wafer 200 from which the reaction gas has desorbed.

[0100] Furthermore, as in the aforementioned film deposition sequence (S3), the adsorption inhibiting gas may be supplied into the processing chamber 201, and then the residual gas may be removed (second step) at the same time. In other words, the second step (residual gas removal) and the supply of the adsorption inhibiting gas into the processing chamber 201 may be performed simultaneously, and the adsorption inhibiting gas may be supplied to the processing chamber 201 while the pressure inside the processing chamber 201 is reduced. This allows the adsorption inhibiting gas to be adsorbed more uniformly onto the wafer 200.

[0101] Furthermore, as described in the aforementioned film deposition sequence (S4, S5), by repeating purging and residual gas removal (second step) a predetermined number of times (one or more times) before and after the step of supplying adsorption-inhibiting gas into the processing chamber 201, the amount of reaction gas adsorbed at specific locations on the wafer 200 can be further reduced. Therefore, the step coverage of the wafer 200 can be improved.

[0102] In the film deposition sequence (S1, S2, S3, S4, S5, etc.), if, for example, NH3 gas is used as the reaction gas and, for example, HCl gas is used as the adsorption inhibitory gas, at least one of the following will be produced as a reaction product: for example, ammonium chloride (NH4Cl), N2, H2, etc. However, this disclosure is not limited to this. For example, the gases described in this disclosure can be used as the respective gases. The reaction product will be the substance produced by the reaction of the gases used.

[0103] By supplying an adsorption-inhibiting gas during the film deposition sequence (S1, S2, S3, S4, S5, etc.), the number of reaction gas molecules adsorbed in multiple layers on the wafer 200 can be reduced. In this way, the adsorption-inhibiting gas not only suppresses the adsorption of raw material gas molecules onto the wafer 200, but also promotes the desorption of reaction gases from the wafer 200. In other words, it modifies the surface state of the wafer 200. Therefore, the adsorption-inhibiting gas used here, i.e., the gas used in post-treatment (adsorption-inhibiting gas), is also called a post-treatment gas, post-treatment gas, treatment gas, modifying gas, or desorption-promoting gas. Furthermore, the adsorption-inhibiting gas supplied before the raw material gas in this disclosure also changes the surface state (surface characteristics, adsorption characteristics) of the wafer 200, so it can also be called a pre-treatment gas, pre-treatment gas, treatment gas, or modifying gas.

[0104] Furthermore, although the above embodiment was described using a gas containing the element Si as the raw material gas as an example, this disclosure is not limited thereto. For example, it may also be applicable to processes using a gas containing at least one element from Group 13, Group 14, Group 4, Group 6, and Group 8 as the raw material gas.

[0105] Furthermore, although the above embodiment described an example in which a gas containing nitrogen is used as the reaction gas, this disclosure is not limited thereto. For example, an oxide film may be formed on the wafer 200 using a gas containing oxygen as the reaction gas. Examples of oxygen-containing gases include oxygen (O2) gas, water (H2O), hydrogen peroxide (H2O2) gas, nitrous oxide (N2O) gas, nitric oxide (NO) gas, and ozone (O3) gas. Alternatively, one or more of these gases may be activated or excited and used as the reaction gas.

[0106] Alternatively, a gas containing hydrogen may be used as the reaction gas to form a film on the wafer 200 with the above element as the main component. Examples of gases containing hydrogen include gases composed of hydrogen, such as hydrogen (H2) gas and deuterium gas, and mononuclear parent hydride gases such as silane gases, borane gases, phosphane gases, and Germanian gases. Alternatively, one or more of these gases may be activated or excited to form the reaction gas. Examples of silane gases include monosilane (SiH4) gas, disilane (Si2H6) gas, and trisilane (Si3H8) gas. Examples of borane gases include monoborane (BH3) gas and diborane (B2H6) gas. Examples of phosphane gases include phosphine (PH3) gas and diphosphine (P2H6) gas. Examples of Germanic gases include monogermanic (GeH4) gas, siegermanic (Ge2H6) gas, and trigermanic (Ge3H8) gas.

[0107] Furthermore, the above embodiments described an example of film deposition using a batch-type vertical substrate processing apparatus that processes multiple substrates at once. However, the disclosure is not limited thereto, and can be suitably applied to film deposition using a single-wafer substrate processing apparatus that processes one or several substrates at once. Even when using these substrate processing apparatuses, film deposition can be performed using the same sequence and processing conditions as in the above embodiments.

[0108] It is preferable to prepare (or have multiple) process recipes (programs describing processing procedures and conditions, etc.) used for forming these various thin films, according to the content of the substrate processing (type of film to be formed, composition ratio, film quality, film thickness, processing procedure, or processing conditions, etc.). When starting the substrate processing, it is preferable to appropriately select an appropriate process recipe from among the multiple process recipes according to the content of the substrate processing. Specifically, it is preferable to pre-store (install) the multiple process recipes prepared individually according to the content of the substrate processing into the storage device 121c of the substrate processing apparatus via a telecommunications line or a recording medium (external storage device 123) that records the process recipes. When starting the substrate processing, it is preferable for the CPU 121a of the substrate processing apparatus to appropriately select an appropriate process recipe from among the multiple process recipes stored in the storage device 121c according to the content of the substrate processing. With this configuration, a single substrate processing apparatus can universally and reproducibly form thin films of various types, composition ratios, film quality, and film thicknesses. Furthermore, it reduces the operator's workload (such as the burden of inputting processing procedures and conditions), allowing for faster commencement of substrate processing while avoiding operator errors.

[0109] Furthermore, this disclosure can also be implemented, for example, by changing the process recipe of an existing substrate processing apparatus. When changing the process recipe, it is possible to install the process recipe relating to this disclosure into the existing substrate processing apparatus via a telecommunications line or a recording medium on which the process recipe is stored, or to change the process recipe itself to the process recipe relating to this disclosure by operating the input / output device of the existing substrate processing apparatus.

[0110] Furthermore, the above embodiments and modifications can be used in combination as appropriate. The processing procedure and processing conditions in this case can be the same as, for example, the processing procedure and processing conditions of the above embodiments and modifications.

[0111] For example, as shown in Figures 6, 7, and 8, there is a region where the amount of adsorption relative to the amount of exposure to the wafer is not saturated. This region may be utilized with at least one of the raw material gas, reaction gas, and adsorption inhibiting gas. Alternatively, for example, the adsorption inhibiting gas (reforming gas) may be supplied after the reaction gas, rather than before the raw material gas. Even with this configuration, one or more of the effects shown in this disclosure can be obtained.

[0112] The embodiments of this disclosure have been described in detail above. However, this disclosure is not limited to the embodiments described above, and can be modified in various ways without departing from its essence. [Explanation of Symbols]

[0113] 10...Substrate processing equipment, 121...Controller, 200...Wafer (substrate), 201...Processing room

Claims

1. a) A step of supplying an adsorption-inhibiting gas to the substrate, b) A step of supplying a raw material gas to the substrate, c) A step of supplying a reaction gas to the substrate, d) The process of forming a film of elements contained in the raw material gas on the substrate by performing a) b) a predetermined number of times as one cycle, with the exposure amount of the raw material gas supplied in b) to the substrate being greater than the exposure amount of the adsorption inhibiting gas supplied in a) to the substrate, It has, b) is, b1) A step of supplying the raw material gas stored in the storage unit to the substrate, b2) A step of stopping the supply of the raw material gas stored in the storage unit, b3) The process includes supplying the raw material gas, which is not stored in the storage unit, to the substrate, b) Perform b1), b2), and b3) in this order. Substrate processing method.

2. In d), the amount of the raw material gas supplied in b) adsorbed onto the substrate is made greater than the amount of the adsorption inhibiting gas supplied in a) adsorbed onto the substrate. The substrate processing method according to claim 1.

3. d) The flow rate of the raw material gas supplied in b) is set to be greater than the flow rate of the adsorption inhibiting gas supplied in a). The substrate processing method according to claim 1.

4. In d), the partial pressure of the raw material gas in the space where the substrate is located in b) is made higher than the partial pressure of the adsorption inhibiting gas in the space where the substrate is located in a). The substrate processing method according to claim 1.

5. d) The supply time of the raw material gas supplied in b) is made longer than the supply time of the adsorption inhibiting gas supplied in a). The substrate processing method according to claim 1.

6. The exposure amount of the adsorption-inhibiting gas shall be the amount at which the improvement in the coverage of the film formed on the substrate in d) saturates. The substrate processing method according to claim 1.

7. The exposure amount of the adsorption-inhibiting gas is set to the amount at which molecules of the adsorption-inhibiting gas saturately adsorb onto the substrate. The substrate processing method according to claim 1.

8. The substrate has a recess, The exposure amount of the adsorption-inhibiting gas is set to the amount at which molecules of the adsorption-inhibiting gas saturately adsorb to the opening side of the recess. The substrate processing method according to claim 1.

9. The amount of exposure to the source gas is set to an amount that does not cause saturation of the adsorption of the source gas molecules onto the substrate. The substrate processing method according to claim 1.

10. The amount of exposure to the reaction gas is set to the amount at which the adsorption of the reaction gas molecules onto the substrate becomes saturated. The substrate processing method according to claim 1.

11. The substrate has a recess, The exposure amount of the adsorption-inhibiting gas shall be such that the step coverage of the film formed in the recess is 70% or more. The substrate processing method according to claim 1.

12. The substrate has a recess, The exposure amount of the adsorption-inhibiting gas shall be such that the difference in step coverage in the depth direction of the film formed in the recess is within 20%. The substrate processing method according to claim 1.

13. a) Adsorbing at least a portion of the halogen element-containing gas onto the substrate in such a way that a portion of the ligand of the source gas is suppressed from being adsorbed onto the substrate. The substrate processing method according to claim 1.

14. a) Adsorbing at least a portion of the adsorption inhibiting gas onto the substrate in such a way that the decomposition products of the raw material gas are suppressed from being adsorbed onto the substrate. The substrate processing method according to claim 1.

15. b) The raw material gas is supplied from two nozzles The substrate processing method according to claim 1.

16. Perform a) before b) The substrate processing method according to claim 1.

17. Perform a) after c). The substrate processing method according to claim 1.

18. After c), the space in which the substrate is located is purged, and a) is performed. The substrate processing method according to claim 17.

19. After performing a) following c), exhaust the space. The substrate processing method according to claim 18.

20. After exhausting the space following c), perform a) again. The substrate processing method according to claim 19.

21. After c), The process of purging the space and performing (a), exhausting the space after (a), and performing (a) again after exhausting the space, is repeated a predetermined number of times. The substrate processing method according to claim 20.

22. After c), the space in which the substrate is located is purged, the space is exhausted, and a) is performed. The substrate processing method according to claim 17.

23. After performing a) following c), the purging and exhaust of the space in which the substrate is located is repeated. The substrate processing method according to claim 17.

24. Between c) and a), the space in which the substrate is present is repeatedly purged and exhausted. The substrate processing method according to claim 23.

25. a) a step of supplying an adsorption inhibiting gas to a substrate, b) A step of supplying a raw material gas to the substrate, c) A step of supplying a reaction gas to the substrate, d) The process of forming a film of elements contained in the raw material gas on the substrate by performing a) b) a predetermined number of times as one cycle, with the exposure amount of the raw material gas supplied in b) to the substrate being greater than the exposure amount of the adsorption inhibiting gas supplied in a) to the substrate, It has, b) is, b1) A step of supplying the raw material gas stored in the storage unit to the substrate, b2) A step of stopping the supply of the raw material gas stored in the storage unit, b3) The process includes supplying the raw material gas, which is not stored in the storage unit, to the substrate, b) Perform b1), b2), and b3) in this order. A method for manufacturing a semiconductor device.

26. a) A procedure for supplying an adsorption inhibiting gas to a substrate, b) A procedure for supplying a raw material gas to the substrate, c) A procedure for supplying a reaction gas to the substrate, d) The procedure of making the exposure of the substrate to the raw material gas supplied in b) greater than the exposure of the substrate to the adsorption inhibiting gas supplied in a), and performing a) b) c) a predetermined number of times as one cycle to form a film of the elements contained in the raw material gas on the substrate, b) is, b1) A procedure for supplying the raw material gas stored in the storage unit to the substrate, b2) A procedure for stopping the supply of the raw material gas stored in the storage unit, b3) A procedure for supplying the raw material gas, which is not stored in the storage unit, to the substrate, b) The procedure is to perform b1), b2), and b3) in this order, A program that causes a circuit board processing unit to execute commands via a computer.

27. ​​A first gas supply system for supplying a raw material gas to a substrate, A second gas supply system that supplies an adsorption-inhibiting gas to the substrate, A third gas supply system for supplying reaction gas to the substrate, A control unit capable of controlling the first gas supply system, the second gas supply system, and the third gas supply system to perform the substrate processing method described in claim 1, A substrate processing apparatus having

28. The supply time of the raw material gas in (b) is shorter than the time in (a). The substrate processing method according to claim 1.

29. The product of the pressure in the processing chamber housing the substrate and the supply time of the raw material gas in b) is, At least one of the pressure and the supply time of the raw material gas in b) is adjusted so that it is greater than the product of the pressure in the processing chamber and the supply time of the adsorption inhibiting gas in a). The substrate processing method according to claim 1.

30. In b3), the raw material gas, which is not stored in the storage section, is supplied to the substrate from the gas supply pipe that supplied the raw material gas in b1). The substrate processing method according to claim 1.

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