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

Abstract

The present invention comprises: a) a step for supplying a first reactant to a substrate having a recess provided with an opening in a side wall, at a first supply amount at which a Knudsen diffusion amount in the opening is less than a prescribed amount; b) a step for supplying a first adsorption inhibitor to the side wall; c) a step for supplying a raw material into the opening; d) a step for supplying a second reactant into the opening; e) a step for performing step b) after step a); and f) a step for performing steps c) and d) a prescribed number of times to preferentially form, within the opening, a film that contains an element contained in the raw material.

Description

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

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

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

[0003] Japanese Patent Publication No. 2023-46964

[0004] In the process of forming a film, the desired film characteristics may not be obtained.

[0005] This disclosure provides a technology capable of improving film properties.

[0006] According to one aspect of the present disclosure, a technology is provided comprising: a) supplying a first reactant to a substrate having a recess with an opening in its side wall in a first supply amount such that the amount of Knudsen diffusion in the opening is less than a predetermined amount; b) supplying a first adsorption inhibitor to the side wall; c) supplying a raw material into the opening; d) supplying a second reactant into the opening; e) performing b) after a); and f) performing c) and d) a predetermined number of times to preferentially form a film containing elements contained in the raw material in the opening.

[0007] According to this disclosure, it is possible to improve film properties.

[0008] This is a schematic diagram of the vertical processing furnace of a substrate processing apparatus according to one embodiment of the present disclosure, showing the processing furnace 202 portion in a vertical cross-sectional view. This is a schematic diagram of a part of the vertical processing furnace of a substrate processing apparatus according to one embodiment of the present disclosure, showing the processing furnace 202 portion in a cross-sectional view along line A-A in Figure 1. This is a schematic diagram of the control unit of a substrate processing apparatus according to one embodiment of the present disclosure, showing the control system in a block diagram. This is a diagram showing an example of a flowchart of a substrate processing process according to one embodiment of the present disclosure. This is a diagram showing an example of a flowchart of a substrate processing process according to one embodiment of the present disclosure. This is a diagram showing an example of a flowchart of a substrate processing process according to one embodiment of the present disclosure. Figure 7(A) is a model diagram of the substrate surface according to one embodiment of the present disclosure, where Figure 7(B) is a model diagram of the substrate surface after treatment with the first reactant, Figure 7(C) is a model diagram of the substrate surface after treatment with the first adsorption inhibitor, Figure 7(D) is a model diagram of the substrate surface after treatment with the second adsorption inhibitor, Figure 7(E) is a model diagram of the substrate surface during the film formation process, and Figure 7(F) is a model diagram of the substrate surface after the film formation process.

[0009] The following explanation will be given with reference to Figures 1 to 7. 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.

[0010] (1) As shown in the configuration diagram 1 of the substrate processing apparatus, the processing furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is mounted vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism that activates the gas with heat.

[0011] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz or silicon carbide (SiC), and is formed in a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 (hereinafter referred to as MF209) is arranged concentrically with the reaction tube 203. The MF209 is made of a metal material such as stainless steel, and is formed in a cylindrical shape with open upper and lower ends. The upper end of the MF209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a is provided between the MF209 and the reaction tube 203 as a sealing member. The reaction tube 203 is installed vertically, similar to the heater 207. The processing vessel (reaction vessel) is mainly composed of the reaction tube 203 and the MF209. A processing chamber 201 is formed in the hollow cylindrical portion of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is carried out within this processing chamber 201.

[0012] Within the processing chamber 201, nozzles 249a to 249e, which serve as the first to fifth supply units, are provided so as to penetrate the side walls of the MF 209. Gas supply pipes 232a to 232e are connected to nozzles 249a to 249e, respectively. Nozzles 249a to 249e are all different nozzles, and nozzles 249b and 249d are each provided adjacent to nozzle 249c. Nozzles 249a and 249e are each provided adjacent to nozzles 249b and 249d on the opposite side from the side adjacent to nozzle 249c.

[0013] Gas supply pipes 232a to 232e are equipped with, in order from the upstream side of the gas flow, mass flow controllers (MFCs) 241a to 241e and valves 243a to 243e, which are flow control devices (flow control units). Downstream of valves 243a to 243e in gas supply pipes 232a to 232e, gas supply pipes 232f to 232j are connected, respectively. Gas supply pipes 232f to 232j are equipped with, in order from the upstream side of the gas flow, MFCs 241f to 241j and valves 243f to 243j, respectively. Gas supply pipes 232a to 232e are made of a metal material such as SUS.

[0014] Nozzles 249a to 249e are provided in an annular space in plan view between the inner wall of the reaction tube 203 and the wafer 200, extending from the lower to the upper part of the inner wall of the reaction tube 203, rising upward in the direction of wafer 200 arrangement. That is, nozzles 249a to 249e are provided in a region horizontally surrounding the wafer arrangement region, on the side of the wafer arrangement region where the wafers 200 are arranged, and are provided along the wafer arrangement region. In plan view, nozzle 249c is positioned to face the exhaust port 231a, described later, in a straight line with respect to the center of the wafer 200 being transported into the processing chamber 201. Nozzles 249b and 249d are positioned to sandwich a straight line L passing through the center of nozzle 249c and the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (outer periphery of the wafer 200). Furthermore, nozzles 249a and 249e are positioned so as to sandwich a straight line L from both sides along the inner wall of the reaction tube 203, on the opposite side from the side adjacent to nozzle 249c of nozzles 249b and 249d. The straight line L is also the straight line passing through nozzle 249c and the center of the wafer 200. In other words, nozzle 249d can be said to be located on the opposite side of nozzle 249b with respect to the straight line L. Similarly, nozzle 249e can be said to be located on the opposite side of nozzle 249a with respect to the straight line L. Nozzles 249b and 249d are arranged symmetrically with respect to the straight line L as the axis of symmetry. Also, nozzles 249a and 249e are arranged symmetrically with respect to the straight line L as the axis of symmetry. Gas supply holes 250a to 250e for supplying gas are provided on the sides of nozzles 249a to 249e, respectively. Each of the gas supply holes 250a to 250e is opened so as to face (oppose) the exhaust port 231a in a plan view, and is configured to supply gas toward the wafer 200. Multiple gas supply holes 250a to 250e are provided extending from the lower to the upper part of the reaction tube 203.

[0015] From the gas supply pipe 232a, the first reactant is supplied as the first gas (first processing gas) into the processing chamber 201 via the MFC 241a, valve 243a, and nozzle 249a.

[0016] From the gas supply pipe 232b, the first adsorption inhibitor is supplied as the second gas (second processing gas) into the processing chamber 201 via the MFC 241b, valve 243b, and nozzle 249b.

[0017] From the gas supply pipe 232c, the raw material is supplied to the processing chamber 201 as the third gas (third processing gas) via the MFC 241c, valve 243c, and nozzle 249c.

[0018] From the gas supply pipe 232d, the second reactant is supplied as the fourth gas (fourth processing gas) into the processing chamber 201 via the MFC 241d, valve 243d, and nozzle 249d.

[0019] From the gas supply pipe 232e, a second adsorption inhibitor, which has a different molecular structure from the first adsorption inhibitor, is supplied to the processing chamber 201 as a fifth gas (fifth processing gas) via the MFC 241e, valve 243e, and nozzle 249e.

[0020] Inert gas is supplied from gas supply pipes 232f to 232j into the processing chamber 201 via MFCs 241f to 241j, valves 243f to 243j, gas supply pipes 232a to 232e, and nozzles 249a to 249e, respectively. The inert gas acts as a purge gas, carrier gas, diluent gas, etc.

[0021] Herein, the term "agent" as used herein 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.

[0022] The processing gas supply system is mainly composed of gas supply pipes 232a to 232e, MFCs 241a to 241e, and valves 243a to 243e. The inert gas supply system is mainly composed of gas supply pipes 232f to 232j, MFCs 241f to 241j, and valves 243f to 243j. In this disclosure, the gas supply system including gas supply pipe 232a, MFC 241a, and valve 243a is also referred to as the first supply system. Gas supply pipe 232f, MFC 241f, and valve 243f may also be considered as part of the first supply system. The gas supply system including gas supply pipe 232b, MFC 241b, and valve 243b is also referred to as the second supply system. Gas supply pipe 232g, MFC 241g, and valve 243g may also be considered as part of the second supply system. Furthermore, the gas supply system including gas supply pipe 232c, MFC 241c, and valve 243c is also referred to as the third supply system. Gas supply pipe 232h, MFC 241h, and valve 243h may also be considered as part of the third supply system. Furthermore, the gas supply system including gas supply pipe 232d, MFC 241d, and valve 243d is also referred to as the fourth supply system. Gas supply pipe 232i, MFC 241i, and valve 243i may also be considered as part of the fourth supply system. Furthermore, the gas supply system including gas supply pipe 232e, MFC 241e, and valve 243e is also referred to as the fifth supply system. Gas supply pipe 232j, MFC 241j, and valve 243j may also be considered as part of the fifth supply system.

[0023] As shown in Figure 1, an exhaust port 231a for exhausting the atmosphere inside the processing chamber 201 is provided at the lower part of the side wall of the reaction tube 203. As shown in Figure 2, in a plan view, the exhaust port 231a is located opposite (facing) the nozzles 249a to 249e (gas supply holes 250a to 250e) with the wafer 200 in between. The exhaust port 231a may be provided along the upper part of the side wall of the reaction tube 203, that is, along the wafer arrangement region. An exhaust pipe 231 is connected to the exhaust port 231a. As shown in Figure 1, a vacuum pump 246, which is a vacuum exhaust device, is connected to the exhaust pipe 231 via a pressure sensor 245, which is a pressure detector (pressure detection unit) for detecting the pressure inside the processing chamber 201, and an APC (Auto Pressure Controller) valve 244, which is a pressure regulator (pressure adjustment unit). The APC valve 244 can be opened and closed while the vacuum pump 246 is operating to evacuate and stop the vacuum evacuation from the processing chamber 201. Furthermore, while the vacuum pump 246 is operating, the valve opening can be adjusted based on the pressure information detected by the pressure sensor 245 to adjust the pressure inside the processing chamber 201. The exhaust system mainly consists of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may also be considered as part of the exhaust system.

[0024] Below the MF209, a seal cap 219 (hereinafter SC219) is provided as a furnace opening cover capable of airtightly closing the lower end opening of the MF209. The SC219 is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220b is provided on the upper surface of the SC219 as a sealing member that contacts the lower end of the MF209. Below the SC219, a rotating mechanism 267 for rotating the boat 217, which will be described later, is installed. The rotating shaft 255 of the rotating mechanism 267 passes through the SC219 and is connected to the boat 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The SC219 is configured to be raised and lowered vertically by a boat elevator 115 (hereinafter BE115), which is a lifting mechanism installed outside the reaction tube 203. BE115 is configured as a transport device (transport mechanism) that moves the SC219 up and down to transport the wafer 200 into and out of the processing chamber 201. Below the MF209, a shutter 219s is provided as a furnace opening cover that can airtightly close the lower end opening of the MF209 when the SC219 has been lowered and the boat 217 has been transported out of the processing chamber 201. The shutter 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that contacts the lower end of the MF209. The opening and closing operation of the shutter 219s is controlled by the shutter opening and closing mechanism 115s.

[0025] The boat 217, which serves as a substrate support, is configured to support multiple wafers 200, for example 25 to 200 wafers 200, in a horizontal position and aligned vertically with their centers aligned, in a multi-stage arrangement, that is, arranged with spacing between them. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, a multi-stage insulation plate 218, also made of a heat-resistant material such as quartz or SiC, is supported.

[0026] A temperature sensor 263 is installed inside the reaction tube 203 as a temperature detector. By adjusting the amount of power supplied to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 is adjusted to the desired temperature distribution. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0027] 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 configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, configured as, for example, a touch panel, is connected to the controller 121.

[0028] The storage device 121c is composed of, for example, flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), etc. The storage device 121c contains, in a readable format, control programs that control the operation of the substrate processing apparatus, and process recipes that describe the procedures and conditions for substrate processing, as described later. The process recipe is a combination of steps in the substrate processing described later that cause the controller 121 to execute and obtain predetermined results, and functions as a program. Hereinafter, process recipes and control programs will be collectively referred to simply as "programs" (program products). Similarly, process recipes will be simply referred to as "recipes." In this disclosure, the term "program" may include only recipes, only control programs, or both. The RAM 121b is configured as a memory area where programs and data read by the CPU 121a are temporarily held.

[0029] The I / O port 121d is connected to the MFCs 241a to 241j, valves 243a to 243j, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotating mechanism 267, BE 115, shutter opening / closing mechanism 115s, etc.

[0030] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to input of operation commands from the input / output device 122. The CPU 121a is configured to control the flow rate adjustment operation of various gases by the MFCs 241a to 241j, the opening and closing operation of valves 243a to 243j, the opening and closing operation of the APC valve 244 and the pressure adjustment operation of the APC valve 244 based on the pressure sensor 245, the starting and stopping of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotating mechanism 267, the raising and lowering operation of the boat 217 by the BE 115, and the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, in accordance with the contents of the read recipe.

[0031] The controller 121 can be configured by installing the above-mentioned program stored in the external storage device 123 onto a computer. The external storage device 123 includes, for example, magnetic disks such as HDDs, optical disks such as CDs, USB memory, and semiconductor memory such as SSDs. 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 disclosure, the term recording media may include only the storage device 121c, only the external storage device 123, or both. The program (program product) may be provided to the computer using communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0032] (2) Substrate Processing Process An example of a processing sequence for forming a film on a substrate as one step in the manufacturing process of a semiconductor device, using the substrate processing apparatus described above, will be explained mainly with reference to Figures 4, 5, 6, and 7. In the following explanation, the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.

[0033] In the substrate processing process (semiconductor device manufacturing process) according to this embodiment, a) a step of supplying a first reactant to a wafer 200 having a recess with an opening in its side wall in a first supply amount such that the amount of Knudsen diffusion in the opening is less than a predetermined amount; b) a step of supplying a first adsorption inhibitor to the side wall; c) a step of supplying raw materials into the opening; d) a step of supplying a second reactant into the opening; e) a step of performing b) after a); and f) a predetermined number of times to preferentially form a film containing elements contained in the raw materials in the opening.

[0034] In this disclosure, the term "wafer" may refer to the wafer itself or to a laminate of a wafer and a predetermined layer or film formed on its surface. In this disclosure, the term "surface of a wafer" may refer to the surface of the wafer itself or to the surface of a predetermined layer formed on the wafer. In this disclosure, the phrase "form a predetermined layer on a wafer" may refer to directly forming a predetermined layer on the surface of the wafer itself or to forming a predetermined layer on top of a layer formed on the wafer. In this disclosure, the term "substrate" has the same meaning as the term "wafer."

[0035] As shown in Figure 7(A), multiple nanosheets 200a1 are formed on the wafer 200 perpendicular to the surface 200a of the wafer 200 at predetermined intervals. Each nanosheet 200a1 has an upper surface 200a6, a lower surface 200a7, and a side wall 200a3. The length w1 in the longitudinal direction (approximately parallel to the wafer surface 200a, also called the in-plane direction of the nanosheet 200a1) of the upper surface 200a6 (lower surface 200a7) of the nanosheet 200a1 is longer than the height h of the side wall 200a3. Of the multiple nanosheets 200a1 provided above the surface 200a of the wafer 200, the uppermost nanosheet 200a1 is called the uppermost surface 200a8. Although not shown, another structure may be provided above the uppermost surface 200a8 (not shown). On the surface 200a of the wafer 200, in the portion facing the lowest nanosheet 200a1, there may be a region 200a9 made of the same material as the nanosheet 200a1, as shown by the dotted line, or there may be no region 200a9. In the following explanation, we will describe the case where the wafer surface 200a is formed of oxide and region 200a9 is not provided. The space between the nanosheets 200a1 is also called the first opening 200a2 (recess 200a2). The first opening 200a2 faces the side wall 200a3 and the bottom 200a4. The side wall 200a3 is also the side wall of the nanosheet 200a1 and is also called the nanosheet side wall 200a3. Furthermore, the region between the upper surface 200a6 and the opposing lower surface 200a7 of the nanosheet 200a1 is a region that opens to the first opening 200a2 (recess 200a2), and is called the second opening 200a5. The second opening 200a5 is also called the region 200a5 in the longitudinal direction of the nanosheet 200a1. The second opening 200a5 is also called the space between nanosheet surfaces 200a5. In other words, the wafer 200 has a recess with an opening in the side wall 200a3.

[0036] Furthermore, as shown in Figure 7(A), the length of the width w1 of the nanosheet 200a1 is greater than the height h of the nanosheet 200a1. Also, the height d1 (also called the nanosheet pitch d1) of the space between nanosheets 200a5 is smaller than the width w1. Also, the height h is smaller than the horizontal distance d2 between the nanosheets 200a1. The relationships of the lengths of each component are (w1 > d2 ≥ d1 ≥ h). Preferably, the relationship is (w1 > d2 > d1 > h). Also preferably, the relationship may be (w1 >> d2 > d1 > h). In such a structure, the space between nanosheets 200a5 has a high aspect ratio with respect to the width of the first opening (horizontal spacing d2 between the nanosheets 200a1), making it difficult for gas molecules to enter the space between nanosheets 200a5. Therefore, there is a challenge in embedding the film between the nanosheet surfaces 200a5.

[0037] (Wafer loading and boat loading, step S1) Once multiple wafers 200 are loaded into the boat 217, the shutter 219s is moved by the shutter opening / closing mechanism 115s, and the lower end opening of the MF 209 is opened. Then, as shown in Figure 1, the boat 217 supporting the multiple wafers 200 is lifted by the BE 115 and loaded into the processing chamber 201. In this state, the SC 219 seals the lower end of the MF 209 via the O-ring 220b.

[0038] (Pressure and temperature adjustment, step S2) The processing chamber 201, i.e., the space where the wafer 200 is located, is evacuated (reduced pressure exhaust) by the vacuum pump 246 so that it reaches the desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is controlled based on this measured pressure information. The wafer 200 inside the processing chamber 201 is also heated by the heater 207 so that it reaches the desired film deposition temperature. At this time, the amount of power supplied to the heater 207 is controlled based on the temperature information detected by the temperature sensor 263 so that the processing chamber 201 has the desired temperature distribution. The rotation of the wafer 200 by the rotation mechanism 267 is also started. The exhaust of the processing chamber 201, the heating of the wafer 200, and the rotation are all continued at least until the processing of the wafer 200 is completed.

[0039] The substrate processing process consists of substrate processing step 1 and substrate processing step 2, as shown in Figures 4 to 6. The surface state of the wafer 200 during substrate processing step 1 and substrate processing step 2 is shown in Figures 7(A) to 7(F).

[0040] (Substrate Processing Process 1, Step S3) In the substrate processing process 1, as shown in Figure 5, there is at least a step A1 of supplying the first reactant, and it may also include a step A2 of purging, a step A3 of count determination, a step A4 of supplying the first adsorption inhibitor, a step A5 of purging, a step A6 of count determination, and a step A7 of count determination, as shown by the dotted line. Each of these steps will be explained below.

[0041] (Step A1: Supply of the first reactant) The first reactant is supplied to the wafer 200 from nozzle 249a. Inert gas may also be supplied from the other nozzles 249b to 249e.

[0042] Specifically, valve 243a is opened, and the first reactant is allowed to flow into the gas supply pipe 232a. The flow rate of the first reactant is adjusted by MFC 241a and supplied into the processing chamber 201 via nozzle 249a. Alternatively, at this time, valves 243g to 243j may be opened, and inert gas may be supplied into the processing chamber 201 via nozzles 249b to 249e, respectively.

[0043] By supplying a modifier (oxidizing agent) as the first reactant to the wafer 200 under the processing conditions in step A1 described below, a region 200b1 where at least a part of the oxidizing agent is adsorbed is formed on the surface of the sidewall 200a3. In the region 200b1, a terminal containing oxygen (O) is formed. When a gas of elemental oxygen is used, an O-terminal is formed. When an O-terminal is formed, the region 200b1 is also referred to as an O-terminal region 200b1. The gas of elemental oxygen is, for example, oxygen (O ２ ) gas, ozone (O ３ ) gas, or a mixed gas thereof. When a gas containing a hydroxy group (OH-group) or a gas capable of generating an OH-group is used as the oxidizing agent, an OH-terminal is formed in the region 200b1. In this case, the region 200b1 is also referred to as an OH-terminal region 200b1. Examples of the gas capable of forming such an OH-terminal include, for example, water (H ２ O), hydrogen peroxide (H ２ O ２ ), hydrogen (H ２ ) + O ２ gas, H ２ + O ３ gas, H ２ O + O ２ , H ２ O + O ３ a gas obtained by activating at least a part of these gases, a gas obtained by mixing two or more of these gases, etc., and at least one of these gases can be used. As shown in Fig. 7(A), when no other structure is provided further above the uppermost nanosheet 200a1, a region 200b2 (indicated by a dotted line) having the same terminal as the region 200b1 may be formed on the uppermost surface 200a8 of the uppermost nanosheet 200a1. The region 200b1 is also referred to as an O-containing region 200b1. As the first reactant, it is preferable to use a gas having a lower reactivity than the second reactant. By using a gas having a lower reactivity, the influence (oxidation) on the underlying nanosheet 200a1 can be reduced.

[0044] Note that in this specification, the combined description of two gases such as "H ２ + O ２ gas" means H２ Gas and O ２ This refers to a mixed gas. When supplying a mixed gas, the two gases may be mixed (premixed) in the supply pipe before being supplied into the processing chamber 201, or the two gases may be supplied separately to the processing chamber 201 from different supply pipes and then mixed (postmixed) within the processing chamber 201.

[0045] Examples of processing conditions in step A1 include: first reactant supply flow rate: 0.1 to 30 slm, inert gas supply flow rate (per gas supply pipe): 0 to 5000 slm, supply time: 0.5 to 30 sec, processing temperature: room temperature to 300°C, and processing pressure: 0.1 to 10 Torr. The processing conditions shown here are examples of conditions that can preferentially form a region 200b1 on the sidewall 200a3 of the nanosheets between the nanosheets 200a1 (second opening 200a5). The diffusion of the first reactant between the nanosheets 200a1 is mainly Knudsen diffusion. The amount of Knudsen diffusion is strongly affected by the supply time when the gas molecule concentration is constant. Therefore, by shortening the supply time in particular, conditions can be created that make it difficult for the first reactant to diffuse into the space between the nanosheets 200a5 (second opening 200a5). Here, the amount of Knudsen diffusion refers to the amount of gas that diffuses into the opening by Knudsen diffusion. Furthermore, the Knudsen diffusion amount may also refer to the amount of gas that reaches a predetermined distance from the opening by Knudsen diffusion. The supply amount of the first reactant is preferably adjusted to a first supply amount such that the amount of Knudsen diffusion within the nanosheet interplane 200a5 is less than a predetermined amount. Here, the predetermined amount means the amount that begins to substantially adsorb within the nanosheet interplane 200a5, as described later. The first supply amount is less than the second supply amount of the second reactant in step B6, which will be described later. The first supply amount is set by at least one of the supply time, supply flow rate, and supply pressure (also called processing pressure) of the first reactant. By adjusting the supply amount of the first reactant to the first supply amount in this way, the nanosheet sidewall 200a3 can be processed preferentially. The supply time of the first reactant is preferably half or less of the supply time of the second reactant, as described later. Furthermore, the pressure in the space where the wafer 200 is located in step A1 (inside the processing chamber 201) is preferably lower than the pressure in the space where the wafer 200 is located in step B6, which will be described later. Lowering the pressure may allow for preferential processing of the sidewall 200a3. Furthermore, it is preferable that the processing temperature in step A1 be lower than the processing temperature in step B6. Lowering the temperature suppresses the impact (oxidation) on the underlying nanosheet 200a1.Furthermore, if the processing temperature is to be lower than that in step B6, a heating step will be provided between substrate processing step 1 and substrate processing step 2.

[0046] Here, numerical ranges such as "1 to 1000 Pa" in this disclosure mean that the lower and upper limits are included within that range. For example, "1 to 1000 Pa" means "1 Pa or more and 1000 Pa or less." The same applies to other numerical ranges. Furthermore, processing temperature refers to the temperature of the wafer 200 or the temperature inside the processing chamber 201, and processing pressure refers to the pressure inside the processing chamber 201. Furthermore, processing time refers to the time during which the processing is continued. Furthermore, gas supply flow rate: 0 sccm means the case in which the gas is not supplied. These also apply in the following explanation.

[0047] The inert gas in this disclosure is, for example, N ２ Alternatively, noble gases such as Ar, He, Ne, and Xe can be used. This also applies to the other steps.

[0048] (Step A2: Purge) Step A2 of the purging process will now be described. In step A2 of the purging process, excess first reactants present on the wafer 200 are removed. This removal of the first reactants can be carried out by at least one of the following steps: supplying an inert gas to the wafer 200, and exhausting the atmosphere in the space where the wafer 200 is located.

[0049] Regarding the supply of inert gas, for example, valve 243f is opened and inert gas is allowed to flow into gas supply pipe 232f. The flow rate of the inert gas is adjusted by MFC 241f and supplied into the processing chamber 201 via nozzle 249a. At this time, any excess first reactant present on the wafer 200 is pushed out by the inert gas. Alternatively, the system may be configured to supply inert gas from other nozzles using a similar procedure.

[0050] Examples of conditions for purging with inert gas supply include: inert gas supply flow rate (per gas supply pipe): 1 to 5000 sccm, supply time: 10 to 60 seconds, and processing pressure: 0.1 to 10 Torr.

[0051] Purge may also be performed by exhausting the atmosphere inside the processing chamber 201 without supplying an inert gas. Such purging can be done by closing each valve in the gas supply pipe and opening the APC valve 244 to a predetermined opening to exhaust the gas.

[0052] (Step A3: Count Determination) In Step A3, it is determined whether Step A1 or Step A1 and Step A2 have been performed a predetermined number of times A. The predetermined number A is 1 or an integer of 2 or more. If the predetermined number A has reached the set number, it is determined as Y, and the process proceeds to the next step A4. On the other hand, if the predetermined number A has not reached the set number, it is determined as N, and the process returns to Step A1.

[0053] Here, it is preferable to set the predetermined number of steps A to an integer of 2 or more. If the first reactant is supplied only once, it may be difficult to perform the modification treatment that forms at least one O-terminant and OH-terminant on the entire side wall 200a3 of the nanosheet (meaning one nanosheet side wall 200a3 and at least one of all of the multiple nanosheet side walls 200a3). This is because increasing the amount supplied of the first reactant may result in at least one O-terminant and OH-terminant being formed on the surfaces within the space between the nanosheets 200a5, thus limiting the amount supplied of the first reactant. Also, if the amount supplied of the first reactant is reduced, a supply shortage may occur, and the first reactant may not reach the side wall 200a3 of the nanosheet 200a1 located on the lower side among the multiple nanosheets 200a1. Therefore, it is preferable to perform step A1 or step A1 and step A2 multiple times with a supply amount that preferentially modifies the nanosheet side walls 200a3 over the space between the nanosheets 200a5. As mentioned above, supplying the material into the space between the nanosheet surfaces 200a5 may be limited by Knudsen diffusion. Therefore, by adjusting the supply time of the first reactant, the sidewalls 200a3 of the nanosheets can be treated preferentially. Furthermore, by performing the treatment multiple times, the first reactant can be supplied to adsorption sites that could not be treated in one go, filling the empty adsorption sites. When supplying the first reactant in pulses, the pulse width corresponds to the supply time. When supplying in pulses multiple times, the interval between pulses corresponds to the purge step A2. The method of supplying the first reactant in multiple steps is also called divided supply. In the case of pulse supply or divided supply, it is preferable to shorten the pulse width (supply time) and increase the supply flow rate (supply pressure, supply concentration) of the first reactant. By configuring it in this way, it becomes possible to preferentially treat the sidewalls 200a3.

[0054] (Step A4: Supply of the first adsorption inhibitor) The supply process of the first adsorption inhibitor (Step A4) will now be described. In Step A4, the first adsorption inhibitor is supplied to the wafer 200 from nozzle 249b. In addition, inert gas may be supplied from nozzles 249a, 249c to 249e, etc., other than nozzle 249b.

[0055] Specifically, valve 243b is opened, and the first adsorption inhibitor is flowed into the gas supply pipe 232b. The flow rate of the first adsorption inhibitor is adjusted by MFC 241b and supplied into the processing chamber 201 via nozzle 249b. At this time, valves 243f to 243j may also be opened, and inert gas may be supplied into the processing chamber 201 via nozzles 249a to 249e, respectively.

[0056] By supplying the first adsorption inhibitor to the wafer 200 (sidewall 200a3) under the processing conditions described in step A4, a region 200c1 is formed on the surface of the sidewall 200a3 where at least a portion of the molecules of the first adsorption inhibitor are adsorbed. In addition, if there are no other structures above the uppermost nanosheet 200a1, a region 200c2 where at least a portion of the molecules of the first adsorption inhibitor are adsorbed may also be formed on the uppermost surface 200a8 of the nanosheet. The region 200c1 is also simply called the first adsorption inhibitor adsorption region 200c1.

[0057] Examples of processing conditions in step A4 include: first adsorption inhibitor supply flow rate (excluding inert gas): 0.01 to 10 g / min, more preferably 0.1 to 5 g / min; inert gas supply flow rate: 100 to 100,000 sccm, more preferably 1,000 to 50,000 sccm; first adsorption inhibitor supply time: 0.5 to 30 seconds; inert gas supply flow rate (per gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm; processing pressure: 10 to 5,000 Pa, more preferably 50 to 1,500 Pa. The processing conditions shown here are examples of conditions that can preferentially form a region 200c1 on the side wall 200a3. It is also preferable to supply the first adsorption inhibitor under conditions that make diffusion of the first adsorption inhibitor into the space between nanosheet surfaces 200a5 difficult. By adjusting the supply amount of the first adsorption inhibitor in this way, the sidewall 200a3 can be treated preferentially. If step A1 is performed before step A4, then O-terminated or OH-terminated ends are formed on the nanosheet sidewall 200a3 by step A1. Since at least a portion of the molecules of the first adsorption inhibitor are more readily adsorbed to such ends, at least a portion of the molecules of the first adsorption inhibitor can be adsorbed preferentially on the nanosheet sidewall 200a3 to form region 200c1.

[0058] The first adsorption inhibitor contains an ether group. As the first adsorption inhibitor containing an ether group, for example, a gas of a compound having the structural formula R-O-R', where R is a branched alkyl group (i.e., a substituent composed of a branched alkane) and R' is a linear hydrocarbon chain can be used. In other words, the first adsorption inhibitor can be a gas of an ether compound having the above-mentioned ligand.

[0059] Furthermore, as the first adsorption inhibitor, the branched alkyl group (R) can be any one selected from the group consisting of isopropyl, isobutyl, sec-butyl, and tert-butyl, or a gas of a compound containing a substituent thereof.

[0060] For the first adsorption inhibitor, a gas of a compound containing any one selected from the group consisting of isobutyl, sec-butyl, and tert-butyl groups, or a substituent thereof, can be suitably used as the branched alkyl group (R) described above.

[0061] As the first adsorption inhibitor, a gas of a compound containing a tert-butyl group or a substituent thereof can be more preferably used as the branched alkyl group (R) as described above. By using a compound having the branched alkyl group with the most branches as R as the first adsorption inhibitor, the effect of inhibiting the adsorption of the raw material can be significantly enhanced compared to branched alkyl groups with two or fewer branches.

[0062] Furthermore, as the first adsorption inhibitor, a gas of a compound containing a linear alkyl group (or acyclic alkyl group) can be used as the linear hydrocarbon chain (R') described above. In other words, as the first adsorption inhibitor, a gas of a compound containing a linear hydrocarbon chain that does not contain unsaturated bonds can be used as the linear hydrocarbon chain (R') described above.

[0063] Furthermore, as the first adsorption inhibitor, a gas of a compound containing a C1-C10 linear alkyl group such as a methyl group (C1), ethyl group (C2), propyl group (C3), n-butyl group (C4), or n-pentyl group (C5) can be used as the linear alkyl group (or acyclic alkyl group) as described above.

[0064] Furthermore, as the first adsorption inhibitor, a gas of a compound containing a linear hydrocarbon chain with an unsaturated bond can be used as the linear hydrocarbon chain (R') described above. Examples of such linear hydrocarbon chains containing an unsaturated bond include linear hydrocarbon chains containing at least one of a double bond and a triple bond, such as a vinyl group, and linear hydrocarbon chains containing at least one of an alkene and an alkyne.

[0065] The first adsorption inhibitor can be a gas of a compound represented by the structural formula R-O-R', which is obtained by arbitrarily selecting and combining the examples of branched alkyl groups (R) and linear hydrocarbon chains (R') described above. For example, the first adsorption inhibitor can be a gas of an ether compound such as isopropyl methyl ether, sec-butyl methyl ether, tert-butyl methyl ether, isopropyl ethyl ether, or tert-butyl ethyl ether. One or more of these compound gases can be used as the first adsorption inhibitor.

[0066] For the first adsorption inhibitor, it is preferable to use a gas of a compound having a molecular weight in the range of 40 to 130 from among the first adsorption inhibitors described above. Furthermore, it is more preferable to use a gas of a compound having a molecular weight in the range of 70 to 110 from among the first adsorption inhibitors described above.

[0067] If the molecular weight is less than 70, the first adsorption inhibitor will not be easily physically adsorbed onto the surface of the wafer 200. In particular, if the molecular weight is less than 40, it may be difficult to physically adsorb the first adsorption inhibitor onto the surface of the wafer 200. Also, if the molecular weight is greater than 110, the diffusion of the molecules of the first adsorption inhibitor in the processing space will be slow, making it difficult for the first adsorption inhibitor to reach deep into the concave structure, and making it difficult to extend the effect of suppressing raw material adsorption to the deeper parts of the concave structure. In particular, if the molecular weight is greater than 130, it may be difficult to get the first adsorption inhibitor to reach deep into the concave structure even if the processing conditions are adjusted. By using a first adsorption inhibitor with a molecular weight of 40 or more, it is possible to induce physical adsorption of the first adsorption inhibitor onto the surface of the wafer 200. By using a first adsorption inhibitor with a molecular weight of 70 or more, it is possible to facilitate physical adsorption of the first adsorption inhibitor onto the surface of the wafer 200. Furthermore, by using a first adsorption inhibitor with a molecular weight of 130 or less, the diffusion rate of the molecules of the first adsorption inhibitor in the processing space can be ensured, making it possible to extend the effect of the first adsorption inhibitor in suppressing the adsorption of raw materials to the deeper parts of the concave structure. By using a first adsorption inhibitor with a molecular weight of 110 or less, it is easy to extend the effect of the first adsorption inhibitor in suppressing the adsorption of raw materials to the deeper parts of the concave structure.

[0068] Furthermore, when using the ether compound gas described above as the first adsorption inhibitor, it is preferable that the surface of the wafer 200 to which the first adsorption inhibitor is supplied is OH-terminated. When the first adsorption inhibitor is supplied to the surface of the OH-terminated wafer 200, the ease of physical adsorption of the first adsorption inhibitor may be improved.

[0069] (Step A5: Purge) Step A5 of the purging process will now be described. In purging step A5, the same process as in purging step A2 is performed. For example, valve 243g is opened and inert gas is flowed into gas supply pipe 232g. The flow rate of the inert gas is adjusted by MFC 241g and supplied into the processing chamber 201 via nozzle 249b. At this time, any excess first adsorption inhibitor present on the wafer 200 is pushed out by the inert gas. Alternatively, the system may be configured to supply inert gas from other nozzles using a similar procedure. The purging conditions can be the same as those for step A2.

[0070] (Step A6: Count Determination Process) In Step A6, it is determined whether Step A4 or Steps A4 and A5 have been performed a predetermined number of times B. The predetermined number B is an integer of 1 or more. If the predetermined number B has reached the set number, it is determined as Y, and the process proceeds to the next step A7. On the other hand, if the predetermined number B has not reached the set number, it is determined as N, and the process returns to Step A4.

[0071] Here, it is preferable to set the predetermined number of steps B to an integer of 2 or more. As the first adsorption inhibitor, as described later, a substance with a relatively large molecular size (for example, an organic substance) may be used. With such a large molecular size, the ligand contained in the molecule acts as steric hindrance. If reacted first adsorption inhibitor is present near an adsorption site in region 200b1 where at least a portion of the material molecules of the first adsorption inhibitor can be adsorbed, the adsorption of at least a portion of the unreacted first adsorption inhibitor molecules may be inhibited (suppressed). Also, if a large amount of reacted first adsorption inhibitor molecules are present in the space where the wafer 200 is located (processing chamber 201), the reacted first adsorption inhibitor may have the effect of inhibiting (suppressing) the adsorption of the unreacted first adsorption inhibitor. By performing the purging step A5, the reacted first adsorption inhibitor present in the processing chamber 201 can be removed, and the unreacted first adsorption inhibitor can be supplied to the adsorption site in region 200b1. Therefore, it is preferable to perform steps A4 and A5 multiple times. Furthermore, by performing step A4 in a pulsed manner over a short period of time, the amount of the first adsorption inhibitor that diffuses into the space between the nanosheet surfaces 200a5 (Knudsen diffusion amount) can be reduced, and at least a portion of the first adsorption inhibitor can be preferentially adsorbed in region 200b1.

[0072] (Step A7: Count Determination Process) In Step A7, it is determined whether Step A1 and Steps A2 to A6 have been performed a predetermined number of times C. The predetermined number C is an integer of 1 or more. If the predetermined number C has reached the set number, it is determined as a Y judgment and the substrate processing process 1 is terminated. If the predetermined number C has not reached the set number, it is determined as an N judgment and the process returns to Step A1.

[0073] Here, the combinations of steps A1 to A7 can be as shown in Figure 5. The more types of steps performed, the higher the processing quality of the fine structure formed on the wafer 200 can be. On the other hand, performing all steps increases the processing time of the substrate processing, including the substrate processing step 1, and reduces the substrate processing throughput. Various options can be selected depending on the performance (characteristics) required for the film formed by the substrate processing.

[0074] (Substrate Processing Process 2, Step S4) Next, the substrate processing process 2 will be described. As shown by the solid lines in Figure 6, the substrate processing process 2 includes a raw material supply step B4, a purging step B5, a second reactant supply step B6, a purging step B7, and a count determination step B8. Alternatively, as shown by the dotted lines, it may be configured to include a second adsorption inhibitor supply step B1, a purging step B2, a count determination step B3, and a count determination step B9. The following will be explained in order according to the flowchart in Figure 6. Note that the raw material supply step B4, the purging step B5, the second reactant supply step B6, the purging step B7, and the count step B8 are also called the film formation process.

[0075] (Step B1: Supply of second adsorption inhibitor) In step B1, the second adsorption inhibitor is supplied to the wafer 200 from nozzle 249e. In addition, an inert gas may be supplied from each of the nozzles 249a to 249d other than nozzle 250e.

[0076] Specifically, valve 243e is opened, and the second adsorption inhibitor is flowed into the gas supply pipe 232e. The flow rate of the second adsorption inhibitor is regulated by MFC 241e and supplied into the processing chamber 201 via nozzle 249e. Alternatively, at this time, valves 243f to 243j may be opened, and inert gas may be supplied into the processing chamber 201 via nozzles 249a to 249e.

[0077] By supplying the second adsorption inhibitor to the wafer 200 under the processing conditions described in step B1, a region 200d1 is formed on the sidewall within the space between the nanosheet planes 200a5 on the upper surface 200a6 and lower surface 200a7 of the nanosheet 200a1, as shown in Figure 7(D), where at least a portion of the molecules of the second adsorption inhibitor are adsorbed. If a region 200a9 is provided on the surface 200a of the wafer 200, a region 200d1 may also be formed on the second opening 200a5 side of region 200a9. Although Figure 7(D) shows the case where region 200d1 is formed only on the second opening 200a5 side, in reality, the adsorption occurs such that the adsorption thickness slopes toward the center of the nanosheet 200a1 (becoming smaller toward the center of the nanosheet 200a1). In this way, the adsorption thickness decreases toward the center of the nanosheet 200a1, which promotes film formation from the center of the nanosheet 200a1 in the film formation process described later. To make the adsorption thickness of the second adsorption inhibitor decrease toward the center of the nanosheet 200a1 in this way, the supply pressure of the second adsorption inhibitor may be made higher than the supply pressure of the first adsorption inhibitor in step A4. The supply pressure is, for example, the pressure inside the processing chamber 201.

[0078] Examples of processing conditions in step B1 include: second adsorption inhibitor supply flow rate (excluding inert gas): 0.01 to 10 g / min, more preferably 0.1 to 5 g / min; inert gas supply flow rate: 100 to 100,000 sccm, more preferably 1,000 to 50,000 sccm; second adsorption inhibitor supply time: 1 to 60 seconds; inert gas supply flow rate (per gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm; processing pressure: 10 to 5,000 Pa, more preferably 50 to 1,500 Pa. The processing conditions shown here are examples of conditions in which the second adsorption inhibitor penetrates inward into the region between nanosheets (nanosheet inter-plane space 200a5) in the vertical direction of the nanosheet 200a1. Furthermore, since diffusion into the space between the nanosheet surfaces 200a5 can occur by Knudsen diffusion, it is preferable that the supply time of the second adsorption inhibitor be longer than that of step A1 and step A4. For example, it is preferable to make it about twice as long as that of step A4. At least a portion of the molecules of the first adsorption inhibitor are adsorbed on the sidewall 200a3 of the nanosheet. This may allow at least a portion of the molecules of the second adsorption inhibitor to fill the empty adsorption sites. Here, empty adsorption sites are areas where at least a portion of the molecules of the first adsorption inhibitor are not adsorbed. Also, at the empty adsorption sites, at least a portion of the molecules of the first adsorption inhibitor inhibit the adsorption of at least a portion of the molecules of the second adsorption inhibitor. Therefore, it is also possible to promote the arrival of the second adsorption inhibitor at the second opening 200a5.

[0079] The second adsorption inhibitor contains an amine group. As the second adsorption inhibitor containing an amine group, a gas containing an organic compound can be used. As the gas containing an organic compound, a gas containing at least one selected from the group consisting of ether compounds, ketone compounds, amine compounds, and organic hydrazine compounds can be used. As the gas containing an ether compound, a gas containing at least one of dimethyl ether, diethyl ether, methyl ethyl ether, propyl ether, isopropyl ether, furan, tetrahydrofuran, pyran, tetrahydropyran, etc. can be used. As the gas containing a ketone compound, a gas containing at least one of dimethyl ketone, diethyl ketone, methyl ethyl ketone, methyl propyl ketone, etc. can be used. As the gas containing an amine compound, a gas containing at least one of methylamine compounds such as monomethylamine, dimethylamine, and trimethylamine; ethylamine compounds such as monoethylamine, diethylamine, and triethylamine; and methylethylamine compounds such as dimethylethylamine and methyldiethylamine can be used. As the gas containing the organic hydrazine compound, a gas containing at least one of the methylhydrazine-based gases such as monomethylhydrazine, dimethylhydrazine, and trimethylhydrazine can be used.

[0080] The type of second adsorption inhibitor may be the same as that of the first adsorption inhibitor, or a different type may be selected. If the same type is used, differences in supply conditions can be used to inhibit (suppress) the adsorption of the raw materials described later at different locations on the nanosheet 200a1. Furthermore, by using different types of materials, it is possible to further suppress the adsorption of raw materials at different locations. Examples of adsorption inhibitors, as disclosed herein, include materials containing ether groups, materials containing amine groups, polymer materials, low molecular weight materials, and halogen-containing materials. Each of these materials has different adsorption characteristics, adsorption suppression characteristics, and desorption characteristics. By using a combination of multiple types of materials, it is possible to achieve the desired film formation.

[0081] (Step B2: Purge) Step B2 of the purge process will now be described. In step B2 of the purge process, the same procedures as in the other purge steps described above are performed. For example, the valve 243j is opened and the inert gas is allowed to flow into the gas supply pipe 232j. The flow rate of the inert gas is adjusted by the MFC 241j and supplied into the processing chamber 201 via the nozzle 249e. At this time, any excess second adsorption inhibitor present on the wafer is pushed out by the inert gas. It is also possible to configure the system to supply inert gas from other nozzles using a similar procedure. The purging conditions can be the same as those for step A2.

[0082] (Step B3: Count Determination Process) In Step B3, it is determined whether Step B1 or Step B1 and Step B2 have been performed a predetermined number of times D. The predetermined number D is an integer of 1 or 2 or more. If the predetermined number D has reached the set number, it is determined as Y, and the process proceeds to the next step B4. On the other hand, if the predetermined number D has not reached the set number, it is determined as N, and the process returns to Step B1.

[0083] Here, the predetermined number of times D is preferably set to an integer of 2 or more if step A4 is not performed or is performed less than the required number of times. If step A4 is not performed or is performed less than the required number of times, a region that sufficiently suppresses the adsorption of raw materials may not be formed on the side wall 200a3. In such cases, by performing the predetermined number of times D as an integer of 2 or more, a region that sufficiently suppresses the adsorption of raw materials can be formed on the nanosheet side wall 200a3. Furthermore, if region 200c1 is formed in substrate processing step 1, the adsorption suppression component of region 200c1 can be reinforced so as to prevent the adsorption suppression component of region 200c1 from being desorbed at some step in the subsequent film formation process (steps B4 to B7).

[0084] (Film Formation Process) Next, the film formation process (steps B4 to B7) will be explained.

[0085] (Step B4: Supply of raw materials) Raw materials are supplied to the wafer 200 from nozzle 249c. Inert gas may be supplied from other nozzles.

[0086] Specifically, valve 243c is opened, and the raw material flows into the gas supply pipe 232c. The flow rate of the raw material is adjusted by MFC 241c and supplied into the processing chamber 201 via nozzle 249c. At this time, valves 243f to 243j may also be opened to supply inert gas into the processing chamber 201 via nozzles 249a to 249e. This supply of inert gas can suppress the backflow of diluent gas and raw material into other gas supply pipes.

[0087] Under the processing conditions described later in step B4, when the raw material is supplied to the wafer 200 (inside the opening), at least a portion of the molecules of the raw material are preferentially adsorbed towards the center of the nanosheet interplanes 200a5, rather than towards the outside of the interplanes 200a5 between the regions 200d1 of the second opening 200a5.

[0088] Examples of processing conditions in step B4 include: raw material supply flow rate (excluding dilution gas): 0.1 to 10 g / min, more preferably 0.5 to 5 g / min; dilution gas supply flow rate: 100 to 100,000 sccm, more preferably 1,000 to 50,000 sccm; raw material supply time: 10 to 600 seconds, more preferably 30 to 300 seconds; inert gas supply flow rate (per gas supply pipe): 0 to 50,000 sccm, more preferably 5,000 to 15,000 sccm; processing temperature: 100 to 600°C, preferably 150 to 300°C; and processing pressure: 0.1 to 10 Torr. The processing conditions shown here are conditions that allow the raw material to be supplied to the center side of the nanosheet interplane 200a5. In other words, these are conditions that promote Knudsen diffusion within the nanosheet interplane 200a5. Here, since at least region 200c1 is formed around the nanosheet 200a1, the adsorption of raw material molecules onto the sidewall 200a3 is suppressed. By suppressing the adsorption of raw material molecules onto the sidewall 200a3, the consumption of raw material on the sidewall 200a3 can be suppressed. As a result, it becomes possible to deliver the raw material to the bottom 200a4 of the first opening 200a2 and into the space between the nanosheet surfaces 200a5.

[0089] As a raw material, a gas containing a molecule having a first element and a ligand bonded to this first element can be used. Examples of the first element include metallic elements and transition metal elements, specifically Group IV elements such as zirconium (Zr), hafnium (Hf), and titanium (Ti). Examples of metallic elements include, in addition to the Group IV elements mentioned above, tantalum (Ta), niobium (Nb), aluminum (Al), molybdenum (Mo), and tungsten (W).

[0090] The first element is a metalloid, such as silicon (Si). In this disclosure, metalloids include Si, boron (B), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0091] Examples of ligands bonded to the first element include organic ligands. Examples of ligands bonded to the first element include at least one of a hydrocarbon group and an amino group. Examples of hydrocarbon groups bonded to the first element include any of the groups selected from the group consisting of alkyl groups such as methyl, ethyl, propyl, and butyl groups, cyclopentadienyl groups, cyclohexadienyl groups, and cycloheptatrielinyl groups, or substituents thereof.

[0092] Examples of raw materials containing Zr as the first element include tetrakisethylmethylaminozirconium (Zr[N(CH) ３ ) C ２ H ５ ] ４ ), tetrakisdiethylaminozirconium (Zr[N(C ２ H ５ ) ２ ] ４ ), tetrakisdimethylaminozirconium (Zr[N(CH ３ ) ２ ] ４ ), Zr (MMP) ４ , Zr(O-tBu) ４ Trisdimethylaminocyclopentadienylzirconium ((C ５ H ５ ) Zr[N(CH ３ ) ２ ] ３Gases such as ) can be used. One or more of these can be used as raw materials.

[0093] Furthermore, as a raw material containing Hf as the first element, for example, tetrakisethylmethylaminohafnium (Hf[N(CH) ３ ) C ２ H ５ ] ４ ), tetrakisdiethylaminohafnium (Hf[N(C) ２ H ５ ) ２ ] ４ ), tetrakisdimethylaminohafnium (Hf[N(CH ３ ) ２ ] ４ ), Hf(O-tBu) ４ , Hf (MMP) ４ , Trisdimethylaminocyclopentadienylhafnium ((C ５ H ５ ) Hf[N(CH ３ ) ２ ] ３ Gases such as ) can be used. One or more of these can be used as raw materials.

[0094] Furthermore, as a raw material containing Ti as the first element, for example, tetrakisethylmethylaminotitanium (Ti[N(CH) ３ ) C ２ H ５ ] ４ ), tetrakisdiethylaminotitanium (Ti[N(C ２ H ５ ) ２ ] ４ ), tetrakisdimethylaminotitanium (Ti[N(CH ３ ) ２ ] ４ ), Ti(O-tBu) ４ Ti (MMP) ４ Trisdimethylaminocyclopentadienyltitanium ((C ５ H ５ )Ti[N(CH ３ ) ２ ] ３ Gases such as ) can be used. One or more of these can be used as raw materials.

[0095] Also, as the first element, as the raw material containing Al, for example, organic gas or inorganic gas can also be used. As the organic gas, triethylaluminum ((C ２ H ５ ) ３ Al), trimethylaluminum ((CH ３ ) ３ Al), dimethylaluminum hydride ((CH ３ ) ２ AlH), dimethylethylamine alanate (AlH ３ N(CH ３ ) ２ C ２ H ５ ) exist. As the inorganic gas, aluminum chloride (AlCl ３ ) exists.

[0096] Also, as the raw material containing Si as the first element, organic gas or inorganic gas can be used. As the organic gas, for example, aminosilane - based gas, that is, a gas containing Si and an amino group can also be used. As the aminosilane - based gas, for example, (dimethylamino) trimethylsilane ((CH ３ ) ２ NSi(CH ３ ) ３ ), diethylaminotrimethylsilane ((C ２ H ５ ) ２ NSi(CH ３ ) ３ ), diethylaminotriethylsilane ((C ２ H ５ ) ２ NSi(C ２ H ５ ) ３ ), dimethylaminotriethylsilane ((CH ３ ) ２ NSi(C ２ H ５ ) ３ ) etc. (dialkylamino) trialkylsilanes, and (diisobutylamino) silane ((C ４ H ９ ) ２ NSiH ３), (diisopropylamino)silane ((C ３ H ７ ) ２ NSiH ３ Mono(dialkylamino)silanes such as ) and (ethylmethylamino)silane (SiH ３ (N(CH ３ ) (C ２ H ５ )), (dimethylamino)silane (SiH ３ (N(CH ３ ) ２ Monoaminosilanes such as ) and trimethoxydimethylaminosilane ((CH ３ ) ２ NSi(OCH) ３ ) ３ ) such trimethoxydialkylaminosilanes, bis(dimethylamino)dimethylsilane ([(CH ３ ) ２ N] ２ Si(CH) ３ ) ２ ) such as bis(dialkylamino)dialkylsilanes and tris(dimethylamino)methylsilane ([(CH ３ ) ２ N] ３ SiCH ３ Tris(dialkylamino)alkylsilanes such as ) and bis(diethylamino)silane ([(C ２ H ５ ) ２ N] ２ SiH ２ ) such as bis(dialkylamino)silanes and bis(tert-butylamino)silane ([(C ４ H ９ )NH] ２ SiH ２ ) and other bis(monoalkylamino)silanes, and tris(dimethylamino)silane ([(CH ３ ) ２ N] ３ Tris(dialkylamino)silanes such as SiH) and tetrakis(dimethylamino)silane ([(CH ３ ) ２ Gases such as tetrakis(dialkylamino)silanes (e.g., N)4Si) can be used.

[0097] As for inorganic gases, tetrachlorosilane (SiCl ４ ) gas, monochlorosilane (SiH ３ Cl) gas, dichlorosilane (SiH ２ Cl ２ ) gas, trichlorosilane (SiHCl ３ ) gases, such as chlorosilane gases, can be used, which do not contain silicon-silicon bonds (i.e., bonds between specific elements) in a single molecule. In addition to chlorosilane gases, inorganic gases such as tetrafluorosilane (SiF) can also be used. ４ ) gas, difluorosilane (SiH ２ F ２ Fluorosilane gases such as ) gas, and tetrabromosilane (SiBr ４ ) gas, dibromosilane (SiH ２ Br ２ Bromosilane-based gases such as ) gas, and tetraiodosilane (SiI ４ ) gas, diiodosilane (SiH ２ I ２ It is also possible to use iodosilane-based gases such as ) gas, which do not contain silicon-silicon bonds (i.e., bonds between specific elements) in a single molecule. ２ Cl ６ ) gas, or octachlorotrisilane (Si ３ Cl ８ ) gas, monochlorodisilane (Si ２ H ５ Cl) gas, dichlorodisilane (Si ２ H ４ Cl ２ ) gas, trichlorodisilane (Si ２ H ３ Cl ３ ) gas, tetrachlorodisilane (Si ２ H ２ Cl ４ ) gas, monochlorotrisilane (Si ３ H ５ Cl) gas, dichlorotricilane (Si ３ H ４ Cl ２As a raw material that can use a chlorosilane-based gas such as ) gas, which contains a bond between Si molecules (i.e., a bond between predetermined elements) in one molecule, one or more of these can be used.

[0098] (Step B5: Purge) Next, the raw materials are purged. Purge step B5 can be performed in the same way as the other purging steps described above. For example, valve 243h is opened and inert gas is flowed into gas supply pipe 232h. The flow rate of the inert gas is adjusted by MFC 241h and supplied into the processing chamber 201 via nozzle 249c. At this time, any excess raw materials present on the wafer 200 are pushed out by the inert gas. It is also possible to configure the system to supply inert gas from other nozzles in the same way. The purging conditions can be the same as those for the other purging steps described above. In this step, it is necessary to purge any unreacted or reacted raw materials present in the nanosheet interplane 200a5. Since the gas supply to the nanosheet interplane 200a5 is rate-limited by Knudsen diffusion, it is preferable that the amount of inert gas supplied be the amount that causes Knudsen diffusion. The amount of Knudsen diffusion can be adjusted mainly by the supply time. Therefore, by making the inert gas supply time longer than the raw material supply time, the amount of inert gas supplied can be increased to exceed the amount of raw material supplied, thereby accelerating the purging of the raw material.

[0099] (Step B6: Supply of the second reactant) Next, the second reactant is supplied to the wafer 200 from nozzle 249d. Inert gas may also be supplied from each of the other nozzles 249a to 249e.

[0100] Specifically, valve 243d is opened, and the second reactant is flowed into the gas supply pipe 232d. The flow rate of the second reactant is adjusted by MFC 241d and supplied into the processing chamber 201 via nozzle 249d. Alternatively, at this time, valves 243f to 243j may be opened, and inert gas may be supplied into the processing chamber 201 via nozzles 249a to 249e.

[0101] Under the processing conditions described in step B6, an oxidizing agent as a second reactant is supplied to the wafer 200 (inside the opening), causing the raw materials adsorbed on the surface of the nanosheet interplane 200a5 to be oxidized and an oxide film to be formed. Since the raw materials are preferentially adsorbed towards the center of the nanosheet 200a1 in the interplane 200a5, the oxide film can be formed from the center of the nanosheet 200a1.

[0102] Examples of processing conditions in step B6 include: second reactant supply flow rate: 1 to 30 slm, inert gas supply flow rate (per gas supply pipe): 0 to 5000 slm, supply time: 1 to 60 sec, and processing pressure: 0.1 to 10 Torr. The processing conditions shown here are examples of conditions that can preferentially supply the second reactant within the plane of the nanosheet 200a1. In this case, the supply amount of the second reactant is set to a second supply amount that makes the amount of Knudsen diffusion within the nanosheet planes 200a5 greater than a predetermined amount. The second supply amount is set by at least one of the supply time, supply flow rate, and supply pressure (also called processing pressure) of the second reactant. Note that the same oxidizing agent as the first reactant can be used as the second reactant. Alternatively, a different oxidizing agent can be used. When using different oxidizing agents, the first reactant can use an oxidizing agent with weaker oxidizing power than the second reactant, and the second reactant can use an oxidizing agent with stronger oxidizing power than the first reactant. An oxidizing agent with weak oxidizing power is, for example, H ２ O, O ２ H ２ +O ２ , at least one of these gases or a combination thereof. On the other hand, a highly oxidizing agent is O ３ H ２ O ２ H ２ +O ２ A gas that has been activated, H ２ O+O ２ A gas that has been activated, H ２ O+O ３ It is at least one of these, or a combination thereof. By using a gas with weaker oxidizing power than the second reactant as the first reactant, the impact (oxidation) on the underlying nanosheet 200a1 can be reduced.

[0103] (Step B7: Purge) The purge step B7 will now be described. The purge step B7 can be performed in the same way as the purge step B5 described above. For example, the valve 243i is opened and the inert gas is allowed to flow into the gas supply pipe 232i. The flow rate of the inert gas is adjusted by the MFC 241i and supplied into the processing chamber 201 via the nozzle 249d. At this time, any excess second reactant present on the wafer 200 is pushed out by the inert gas. Alternatively, the system may be configured to supply the inert gas from other nozzles in the same way. The purging conditions can be the same as those for the purge step B5 described above.

[0104] (Step B8: Count Determination Process) In Step B8, it is determined whether Steps B4 to B7 have been performed a predetermined number of times E. The predetermined number E is an integer of 1 or more. If the predetermined number E has reached the set number, it is determined as Y, and the process proceeds to the next step. If the predetermined number E has not reached the set number, it is determined as N, and the process returns to Step B4.

[0105] (Step B9: Count Determination Process) In Step B9, it is determined whether the set step from Steps B1 to B8 has been performed a predetermined number of times F. The predetermined number F is an integer of 1 or more. If the predetermined number F has reached the set number, a Y determination is made and the substrate processing process 2 is terminated. If the predetermined number F has not reached the set number, an N determination is made and the process returns to Step B1.

[0106] Here, it is preferable to set at least one of the predetermined number of repetitions E and the predetermined number of repetitions F to an integer of 2 or more. By setting it in this way and performing the process multiple times, a film 200e1 can be formed between the nanosheets 200a1 as shown in Figure 7(E), and finally, a film 200f1 can be formed around the nanosheets 200a1 as shown in Figure 7(F). When the predetermined number of repetitions E is set to an integer of 2 or more, it becomes possible to deposit the film between the planes of the nanosheets 200a1 while removing regions where raw materials are difficult to adsorb, such as regions 200c1 and 200d1 formed around the nanosheets 200a1 as shown in Figures 7(D) and 7(E). On the other hand, by setting the predetermined number of repetitions F to an integer of 2 or more, the second adsorption inhibitor can be replenished in step B1 to the regions 200c1 and 200d1 that are removed in the film formation process (steps B4 to B7), thereby promoting the deposition of the film 200e1 between the planes of the nanosheets 200a1. Furthermore, both the predetermined number of repetitions E and the predetermined number of repetitions F may be set to integers of 2 or more. Also, as shown in Figure 7(E), after a certain amount of film 200e1 has been formed between the planes of the nanosheet 200a1, the setting of the predetermined number of repetitions F may be changed to "1". In other words, the supply of the second adsorption inhibitor may be stopped in the middle of the film formation process. By configuring it in this way, each time the number of times the film formation process is performed increases, regions 200c1 and 200d1 are removed, and as shown in Figure 7(F), ultimately, a film 200f1 can be formed around the nanosheet 200a1 such that regions 200c1 and 200d1 are eliminated.

[0107] After the substrate processing step 2, as shown in Figure 4, a purging step (step S5) and a wafer removal step (step S6) are performed.

[0108] (Purge, step S5) After the processing of the wafer 200 is completed, N as a purge gas is released from each of the nozzles 249a to 249e. ２Gas is supplied into the processing chamber 201 and exhausted through the exhaust port 231a. This purges the processing chamber 201, removing any remaining gas and reaction by-products (purging). Subsequently, the atmosphere inside the processing chamber 201 is replaced with an inert gas, and the pressure inside the processing chamber 201 is returned to atmospheric pressure. The output to the heater 207 is also adjusted to perform a cooling process to lower the temperature of the wafer 200. The temperature of the wafer 200 is adjusted to a temperature at which it can be removed from the processing chamber 201.

[0109] (Wafer removal, step S6) The SC219 is lowered by the BE115, and the lower end of the MF209 is opened. The processed wafer 200 is then removed from the reaction tube 203 through the lower end of the MF209 while supported by the boat 217. After the boat is removed, the shutter 219s is moved, and the lower end opening of the MF209 is sealed by the shutter 219s via the O-ring 220c. After the processed wafer 200 has been removed from the reaction tube 203, it is removed from the boat 217.

[0110] In this manner, the substrate processing process is carried out.

[0111] (3) Effects of this embodiment According to this embodiment, one or more of the following effects can be obtained: (a) to (j).

[0112] (a) By performing step A1, the adsorption of at least one of the first adsorption inhibitor and the second adsorption inhibitor onto the side wall 200a3 can be promoted. At least one of the first adsorption inhibitor and the second adsorption inhibitor suppresses film formation on the side wall 200a3, and a film can be preferentially formed between the planes of the nanosheet 200a1.

[0113] (b) By performing steps A1 and A2 a predetermined number of times, the density of at least one of the O-terminated and OH-terminated particles formed on the side wall 200a3 can be improved. As a result, the adsorption of at least one of the first adsorption inhibitor and the second adsorption inhibitor can be promoted.

[0114] (c) After performing step A1, step A4 can be performed to promote the adsorption of the first adsorption inhibitor onto the side wall 200a3.

[0115] (d) After performing step A1, steps A4 and A5 can be performed a predetermined number of times to increase the density of the first adsorption inhibitor on the side wall 200a3.

[0116] (e) By performing steps A1 and A2 a predetermined number of times, and steps A4 and A5 a predetermined number of times, the density of the first adsorption inhibitor on the side wall 200a3 can be improved.

[0117] (f) By performing steps A1, A2, A4, and A5 a predetermined number of times, the density of the first adsorption inhibitor on the side wall 200a3 can be increased.

[0118] (g) After performing the substrate processing step 1, the film formation steps B4 to B7 are carried out to preferentially form a film between the planes of the nanosheet 200a1.

[0119] (h) After performing the substrate processing step 1, step B1 is performed a predetermined number of times, and a film deposition step is performed, thereby allowing a film to be preferentially formed between the planes of the nanosheet 200a1.

[0120] (i) After performing the substrate processing step 1, steps B1 and B2 are performed a predetermined number of times, and then a film formation step is performed, thereby allowing a film to be preferentially formed between the planes of the nanosheet 200a1.

[0121] (j) After performing the substrate processing step 1, by performing steps B1 and B2 and the film formation step a predetermined number of times, a film can be preferentially formed between the planes of the nanosheet 200a1.

[0122] <Second Embodiment (Another Aspect of the Disclosure)>

[0123] In the first embodiment described above, an example was described in which substrate processing step 1 and substrate processing step 2 are performed. In contrast, in another aspect of the present disclosure, a substrate processing step 3 may be performed as a further pre-treatment before performing substrate processing step 1.

[0124] (Substrate processing step 3) This step involves applying H-termination treatment to at least one of the upper surface 200a6, lower surface 200a7, and side wall 200a3 of the nanosheet 200a1. By performing H-termination, it is possible to form terminations that promote the adsorption of raw materials onto the nanosheet 200a1. Preferably, the entire surface of the nanosheet 200a1 (upper surface 200a6, lower surface 200a7, and side wall 200a3) is subjected to H-termination treatment. After performing H-termination treatment, the substrate processing step 1 is performed so that the nanosheet side wall 200a3 has at least one or more terminations, such as O terminations and OH terminations, and the upper surface 200a6 and lower surface 200a7 of the nanosheet 200a1 have H terminations. As a result, at least a portion of the first adsorption inhibitor is adsorbed on the side wall 200a3, and the adsorption of raw materials can be promoted on the upper surface 200a6 and lower surface 200a7. This promotes film formation between the planes of the nanosheet 200a1. In other words, the same effects as in the above-described embodiment can be obtained in this embodiment as well. As for the H termination treatment, H ２ Gas, deuterium (D ２ This can be done by supplying at least one of the following: gases, activated gases, etc.

[0125] Furthermore, although the above-described embodiment described an example in which steps B4 to B7 are performed as a film formation process, it is not limited to this. The same effects as in the above-described embodiment can be obtained even when steps A4, A5, and steps B4 to B7 are performed a predetermined number of times as a film formation process.

[0126] Furthermore, in the above-described embodiment, an example was given in which steps B1 to B3 are performed before the film deposition process (steps B4 to B7) as the substrate processing step 2, but the invention is not limited to this. Even when steps A1 or steps A1 to A3 and steps B1 to B3 are performed in this order a predetermined number of times as the substrate processing step 2 before the film deposition process, the same effects as in the above-described embodiment can be obtained.

[0127] In the embodiments described above, an example of forming an oxide film containing the first element was explained, but the invention is not limited to this. A nitride film can be formed by using at least a nitride agent (nitrogen-containing gas) as the second reactant. Examples of nitride agents include ammonia (NH₄). ３ ) gas, diazene (N ２ H ２ ) gas, hydrazine (N ２ H ４ Hydrogen nitride-based gases such as ) gas can be used. In addition, as the N-containing gas, for example, N activated by plasma excitation can be used. ２ Gas (N ２ ＊ (gas) or the above-mentioned hydrogen nitride-based gases (e.g., NH ３ ＊ Gases, etc., can be used. One or more of these can be used as the nitrider.

[0128] Furthermore, although the above-described embodiment described an example of forming an oxide film containing a first element, the method is not limited to this. It can also be applied when forming an oxide film containing a second element in addition to the first element. The second element is, for example, a different element from the first element. For example, the first element may be selected from group 4 elements, and the second element may be selected from group 13 elements and group 14 elements, and the film formation process may be carried out using gases containing each of these elements. For example, films such as TiSiO, TiAlO, HfAlO, HfSiO, ZrAlO, and ZrSiO can be formed.

[0129] 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, 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 be used to form thin films of various types, composition ratios, film quality, and film thickness in a general-purpose and reproducible manner. Furthermore, it reduces the operator's workload (such as the burden of inputting processing procedures and conditions), allowing for quicker initiation of substrate processing while avoiding operational errors.

[0130] 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.

[0131] Furthermore, this disclosure can be used, for example, in the manufacturing process of NAND flash memory, DRAM, LOGIC, etc., which have a three-dimensional structure.

[0132] The above-described embodiments illustrate an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at once. This disclosure is not limited to the above-described embodiments and can be suitably applied, for example, to forming a film using a single-wafer substrate processing apparatus that processes one or several substrates at once. Furthermore, the above-described embodiments illustrate an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace. This disclosure is not limited to the above-described embodiments and can be suitably applied to forming a film using a substrate processing apparatus having a cold-wall type processing furnace.

[0133] Even when using these substrate processing devices, each process can be carried out using the same processing procedures and conditions as described above, and the same effects as described above can be obtained.

[0134] The above-described 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-described embodiments and modifications.

[0135] 200 Wafer (substrate) 200a2 First opening (recess) 200a3 Side wall 200a5 Second opening

Claims

1. A substrate processing method comprising: a) supplying a first reactant to a substrate having a recess with an opening in its side wall in a first supply amount such that the amount of Knudsen diffusion in the opening is less than a predetermined amount; b) supplying a first adsorption inhibitor to the side wall; c) supplying a raw material into the opening; d) supplying a second reactant into the opening; e) performing b) after a); and f) performing c) and d) a predetermined number of times to preferentially form a film containing elements contained in the raw material in the opening.

2. The substrate processing method according to claim 1, wherein the supply amount of the second reactant is set to a second supply amount such that the amount of Knudsen diffusion in the opening is greater than a predetermined amount.

3. The substrate processing method according to claim 2, wherein the first supply amount is less than the second supply amount.

4. The substrate processing method according to any one of claims 1 to 3, wherein the first supply amount is set by at least one of the supply time, supply flow rate, and supply pressure of the first reactant.

5. The substrate processing method according to claim 2 or 3, wherein the second supply amount is set by at least one of the supply time, supply flow rate, and supply pressure of the second reactant.

6. The substrate processing method according to claim 1, wherein step b), c), and d) are performed a predetermined number of times in step f).

7. e) is the substrate processing method according to claim 1, wherein a) and b) are performed in this order a predetermined number of times.

8. a) The substrate processing method according to claim 1, wherein the first reactant is supplied a predetermined number of times.

9. The substrate processing method according to claim 8, wherein the supply of the first reactant is performed by pulse supply a predetermined number of times.

10. b) The substrate processing method according to claim 1 or 6, wherein the first adsorption inhibitor is supplied a predetermined number of times.

11. The substrate processing method according to claim 10, wherein the supply of the first adsorption inhibitor is performed by pulse supply a predetermined number of times.

12. g) A step of supplying a second adsorption inhibitor having a molecular structure different from the first adsorption inhibitor into the opening; h) A step of performing a) and g) in this order a predetermined number of times, the substrate processing method according to claim 1.

13. The substrate processing method according to claim 1, further comprising the steps of g) supplying a second adsorption inhibitor having a molecular structure different from the first adsorption inhibitor into the opening, wherein in f) g) c) d) are performed in this order.

14. The substrate treatment method according to claim 1, wherein the first adsorption inhibitor comprises an ether group.

15. The substrate treatment method according to claim 12 or 13, wherein the second adsorption inhibitor comprises an amine group.

16. The substrate treatment method according to claim 1, wherein the first reactant is the same oxidizing agent as the second reactant.

17. The substrate treatment method according to claim 1, wherein the first reactant is an oxidizing agent with weaker oxidizing power than the second reactant.

18. A method for manufacturing a semiconductor device, comprising: a) supplying a first reactant to a substrate having a recess with an opening in its side wall in a first supply amount such that the amount of Knudsen diffusion in the opening is less than a predetermined amount; b) supplying a first adsorption inhibitor to the side wall; c) supplying a raw material into the opening; d) supplying a second reactant into the opening; e) performing b) after a); and f) performing c) and d) a predetermined number of times to preferentially form a film containing elements contained in the raw material in the opening.

19. A program that causes a substrate processing apparatus to perform the following steps via computer: a) supplying a first reactant to a substrate having a recess with an opening in its side wall at a first supply amount such that the amount of Knudsen diffusion in the opening is less than a predetermined amount; b) supplying a first adsorption inhibitor to the side wall; c) supplying a raw material into the opening; d) supplying a second reactant into the opening; e) performing b) after a); and f) performing c) and d) a predetermined number of times to preferentially form a film containing elements contained in the raw material in the opening.

20. A substrate processing apparatus comprising: a first supply system for supplying a first reactant to a substrate having a recess with an opening in its side wall; a second supply system for supplying a first adsorption inhibitor to the substrate; a third supply system for supplying raw materials to the substrate; a fourth supply system for supplying a second reactant to the substrate; a control unit configured to control the first supply system, the second supply system, the third supply system, and the fourth supply system so as to perform the following: a) supplying the first reactant to the substrate having a recess and an opening in the side wall of the recess at a first supply amount such that the amount of Knudsen diffusion in the opening is less than a predetermined amount; b) supplying the first adsorption inhibitor to the side wall; c) supplying raw materials into the opening; d) supplying a second reactant into the opening; e) performing b) after a); and f) performing c) and d) a predetermined number of times to preferentially form a film containing elements contained in the raw materials in the opening.

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