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

Abstract

This invention provides a substrate processing method, a semiconductor device manufacturing method, a process article, and a substrate processing apparatus capable of selectively removing a film formed in a recess using a processing liquid. The method includes the following steps: (a) preparing a substrate, wherein the substrate includes a first film formed in a recess, and the surface of the first film in the recess is sealed by a first end cap that reduces its wettability to the processing liquid; and (b) supplying the processing liquid to the substrate, selectively exposing the surface of the first film formed in a first region on the opening side of the recess to the processing liquid relative to the surface of the first film formed in a second region on the bottom side of the recess, thereby removing at least a portion of the first film formed in the first region while retaining residual first film in the second region.

Description

Technical Field

[0001] This disclosure relates to a substrate processing method, a semiconductor device manufacturing method, a process article, and a substrate processing apparatus. Background Technology

[0002] As a step in the manufacturing process of a semiconductor device, sometimes a process is performed to remove (etch) the surface formed in the recess of the substrate (for example, see Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: WO2019 / 003662 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] This disclosure provides a technique for selectively removing films formed in recesses using a processing liquid.

[0008] Solution for solving the problem

[0009] According to one aspect of this disclosure, a technique is provided, comprising the following steps:

[0010] (a) Preparing a substrate, wherein the substrate includes a first film formed in a recess, the surface of the first film in the recess being sealed by a first sealing end that reduces wettability to a processing liquid; and

[0011] (b) The processing liquid is supplied to the substrate, and the surface of the first film formed in the first region on the opening side of the recess is selectively exposed to the processing liquid relative to the surface of the first film formed in the second region on the bottom side of the recess, thereby removing at least a portion of the first film formed in the first region while retaining the residual first film formed in the second region.

[0012] Invention Effects

[0013] According to this disclosure, a processing solution can be used to selectively remove the film formed in the recess. Attached Figure Description

[0014] Figure 1 This is a schematic structural diagram of the substrate processing apparatus 100 applicable to various embodiments of this disclosure.

[0015] Figure 2 This is a schematic structural diagram of the vertical processing furnace of the film forming apparatus 500 included in the substrate processing apparatus 100 applicable to various embodiments of this disclosure, and is a diagram showing the processing furnace 202 portion in a longitudinal sectional view.

[0016] Figure 3 This is a schematic structural diagram of the vertical processing furnace of the film deposition apparatus 500 included in the substrate processing apparatus 100 applicable to various embodiments of this disclosure. Figure 2 The AA-line sectional view shows part of the processing furnace 202.

[0017] Figure 4 A schematic structural diagram of the removal device 600 included in the substrate processing apparatus 100 applicable to various embodiments of this disclosure.

[0018] Figure 5 This is a schematic structural diagram of the controller 121 of the substrate processing apparatus 100 applicable to various embodiments of this disclosure, and is a block diagram representing the control system of the controller 121.

[0019] Figure 6 This is a diagram illustrating the area of ​​the recess provided on the surface of wafer 200 in various embodiments of this disclosure.

[0020] Figure 7 (a) to (j) are schematic cross-sectional views of the surface of the wafer 200 with a recess in the first embodiment of this disclosure. Figure 7 (a) is a partial schematic diagram of wafer 200 after the (first) formation of the first film. Figure 7 (b) is a partial schematic diagram of wafer 200 after the first end cap is formed (for the first time). Figure 7 (c) is a partial schematic diagram of wafer 200 after a portion of the first film has been selectively removed (for the first time). Figure 7 (d) is a partial schematic diagram of wafer 200 after the first end cap has been removed from the surface of the first film. Figure 7 (e) is a partial schematic diagram of wafer 200 after the (second) formation of the first film. Figure 7 (f) is a partial schematic diagram of wafer 200 after the first film has been formed and the first end cap has been formed (the second time). Figure 7 (g) is a partial schematic diagram of wafer 200 after a portion of the first film has been selectively removed (for the second time). Figure 7 (h) is a partial schematic diagram of wafer 200 after the first end cap has been removed from the surface of the first film. Figure 7 (i) is a partial schematic diagram of wafer 200 after the (third) formation of the first film. Figure 7 (j) is a partial schematic diagram of wafer 200 after the first end capping is formed (the third time).

[0021] Figure 8 (a) to (c) are schematic cross-sectional views of the surface of the wafer 200 with a concave portion in a variation 1 of the first embodiment of the present disclosure. Figure 8(a) is a partial schematic diagram of wafer 200 after the (first) formation of the first film. Figure 8 (b) is a partial schematic diagram of wafer 200 after an oxide layer has been formed on the surface of the first film. Figure 8 (c) is a partial schematic diagram of wafer 200 after the first end cap is formed (for the first time).

[0022] Figure 9 (a) and (b) are schematic cross-sectional views of the surface portion of the wafer 200 with a concave portion in a variation 2 of the first embodiment of the present disclosure. Figure 9 (a) is a partial schematic diagram of wafer 200 after the (first) formation of the first film with the first end cap. Figure 9 (b) is a partial schematic diagram of wafer 200 after a portion of the first film has been selectively removed (for the first time).

[0023] in:

[0024] 200 — wafer (substrate). Detailed Implementation

[0025] <The First Proposal of This Disclosure>

[0026] The first aspect of this disclosure will now be described with reference to the accompanying drawings. Furthermore, the drawings used in the following description are schematic, and the dimensional relationships and ratios of the elements shown may not necessarily reflect reality. Additionally, the dimensional relationships and ratios of the elements may not be consistent across different drawings.

[0027] (1) Structure of the substrate processing apparatus 100

[0028] like Figure 1 As shown, the substrate processing apparatus 100 mainly includes a film forming apparatus 500, a removal apparatus 600, and a transfer chamber 700.

[0029] The film deposition apparatus 500 is the apparatus for performing film deposition on the wafer 200 in the substrate processing steps described later. The removal apparatus 600 is the apparatus for performing removal (etching) on ​​the wafer 200 in the substrate processing steps described later. The transport chamber 700 is the area where the wafer 200 is transported between the film deposition apparatus 500 and the removal apparatus 600.

[0030] (i) Structure of film forming apparatus 500

[0031] like Figure 2 As shown, the processing furnace 202 has a heater 207 that serves as a temperature adjustment unit (heating unit). The heater 207 also functions as an activation mechanism (activation unit) that uses heat to activate (excite) the gas.

[0032] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is formed into a cylindrical shape that is closed at the top and open at the bottom. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. An O-ring 220a, serving as a sealing component, is provided between the manifold 209 and the reaction tube 203. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow part of the cylindrical part of the processing container. The processing chamber 201 is configured to accommodate a wafer 200, which serves as a substrate. The wafer 200 is processed within this processing chamber 201.

[0033] Nozzles 249a-249c, serving as the first to third supply units, are respectively installed within the processing chamber 201, penetrating the side wall of the manifold 209. Gas supply pipes 232a-232c are connected to nozzles 249a-249c respectively.

[0034] In gas supply pipes 232a-232c, mass flow controllers (MFCs) 241a-241c (flow controllers) and valves 243a-243c (on / off valves) are sequentially installed from the upstream side of the airflow. Gas supply pipe 232d is connected downstream of valve 243a in gas supply pipe 232a. Gas supply pipe 232e is connected downstream of valve 243b in gas supply pipe 232b. Gas supply pipe 232f is connected downstream of valve 243c in gas supply pipe 232c. In gas supply pipes 232d-232f, MFCs 241d-241f and valves 243d-243f are sequentially installed from the upstream side of the airflow.

[0035] like Figure 3 As shown, nozzles 249a-249c are respectively positioned upright in the space between the inner wall of the reaction tube 203 and the wafer 200, extending upwards from the lower part of the reaction tube 203 towards the wafer 200 in the alignment direction. Gas supply holes 250a-250c are respectively provided on the sides of the nozzles 249a-249c for supplying gas. The gas supply holes 250a-250c open opposite (face-to-face) to the exhaust port 231a when viewed from above, allowing gas to be supplied towards the wafer 200. Multiple gas supply holes 250a-250c are provided from the lower to the upper part of the reaction tube 203.

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

[0037] At least one of a first reactant and a second reactant is supplied into the processing chamber 201 from the gas supply pipe 232b via MFC 241b, valve 243b, and nozzle 249b. The first reactant and the second reactant are used as one of the film-forming agents.

[0038] At least one of a third reactant and a modifier is supplied from gas supply pipe 232c into processing chamber 201 via MFC 241c, valve 243c, and nozzle 249c. The third reactant is used as one of the film-forming agents.

[0039] Inactive gases are supplied to the treatment chamber 201 from gas supply pipes 232d to 232f via MFCs 241d to 241f, valves 243d to 243f, gas supply pipes 232a to 232c, and nozzles 249a to 249c. These inactive gases function as purge gases, carrier gases, and dilution gases.

[0040] A plasma excitation unit, or remote plasma unit (RPU) 270, is provided downstream of the connection between the gas supply pipe 232b and the gas supply pipe 232e. This unit is designed to excite matter into a plasma state. The RPU 270 can excite matter by plasmaizing it internally by applying high-frequency (RF) power.

[0041] RPU270 is configured to excite a substance (e.g., a first reactant) supplied from gas supply pipe 232b into a plasma state and supply it as plasma-excited substance into processing chamber 201.

[0042] The raw material supply system mainly consists of gas supply pipe 232a, MFC 241a, and valve 243a. The reaction body (first reaction body, second reaction body) supply system mainly consists of gas supply pipe 232b, MFC 241b, and valve 243b. The reaction body (third reaction body) supply system or modifier supply system mainly consists of gas supply pipe 232c, MFC 241c, and valve 243c. The inactive gas supply system mainly consists of gas supply pipes 232d~232f, MFC 241d~241f, and valves 243d~243f. Alternatively, the raw material supply system and the reaction body supply system may be combined and referred to as the film-forming agent supply system. Nozzles connected to the gas supply pipes constituting the above-mentioned supply systems may also be included in this supply system.

[0043] An exhaust port 231a is provided below the side wall of the reaction tube 203 for venting the atmosphere inside the processing chamber 201. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246, which serves as a vacuum venting device, is connected to the exhaust pipe 231 via a pressure sensor 245 (which acts as a pressure detector, pressure detection unit) and an APC (Auto Pressure Controller) valve 244 (which acts as a pressure regulator, pressure adjustment unit). The APC valve 244 is configured such that by opening and closing the valve while the vacuum pump 246 is operating, vacuum venting and vacuum venting cessation can be performed inside the processing chamber 201. Furthermore, by adjusting the valve opening based on the pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating, the pressure inside the processing chamber 201 can be adjusted. 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 included in the exhaust system.

[0044] A sealing cover 219, serving as a furnace opening cover, is provided below the manifold 209 to airtightly seal the lower opening of the manifold 209. An O-ring 220b, serving as a sealing component, is provided on the upper surface of the sealing cover 219, abutting against the lower end of the manifold 209. A rotation mechanism 267, for rotating the wafer boat 217, is provided below the sealing cover 219. The rotation shaft 255 of the rotation mechanism 267 is connected to the wafer boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the wafer boat 217. The wafer boat elevator 115, serving as a lifting mechanism, is configured as a conveying device (transfer mechanism) for moving the wafer 200 in and out of the processing chamber 201 by raising and lowering the sealing cover 219.

[0045] The crystal boat 217, which serves as a substrate support, is configured to support multiple wafers 200, for example 25 to 200, arranged horizontally and aligned with each other in a vertical direction in multiple layers, i.e., arranged at intervals. Heat insulation plates 218 are supported in multiple layers at the bottom of the crystal boat 217.

[0046] A temperature sensor 263, which functions as a temperature detector, is installed inside the reaction tube 203. The energizing status of the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, thereby achieving the desired temperature distribution within the processing chamber 201.

[0047] (ii) Structure of the removal device 600

[0048] like Figure 4As shown, the removal apparatus 600 includes a processing tank 610. The processing tank 610 can hold one or more wafers 200. A processing liquid supply pipe 640 is connected to a processing liquid tank (not shown) via a liquid mass flow controller (LMFC) 650 and is configured to supply processing liquid into the processing tank 610. The processing tank 610 stores processing liquid for exposure and immerses the wafers 200 in it. The processing liquid supply pipe 640 and the LMFC 650 constitute a processing liquid exposure system for exposing the wafers 200 to the processing liquid (it can also be called a processing liquid supply system for supplying processing liquid to the wafers 200). The processing liquid exposure system may further include the processing tank 610. The removal apparatus 600 includes a temperature sensor 620 for detecting the temperature of the processing liquid and a heater 630 for adjusting the temperature of the processing liquid. The temperature sensor 620 is disposed along the inner wall of the processing tank 610. The heater 630 is located near the processing tank 610 and is configured to maintain the processing liquid in the processing tank 610 at an appropriate temperature based on the temperature detected by the temperature sensor 620.

[0049] (iii) Structure of the transport room 700

[0050] like Figure 1 As shown, a transfer chamber 700 is configured between the film deposition apparatus 500 and the removal apparatus 600 via gate valves 10a and 10b. A transfer mechanism 750 for transporting wafers 200 is provided within the transfer chamber 700. The transfer mechanism 750 places the wafers 200 on a substrate mounting portion provided on the arm, and performs wafer 200 transfer between the film deposition apparatus 500 and the removal apparatus 600.

[0051] (iv) Control Department

[0052] like Figure 5As shown, the controller 121, which serves as the control unit (control mechanism) for the film-forming apparatus 500, the removal apparatus 600, and the transfer chamber 700, is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a storage device 121c, and an 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, such as a touch panel, is connected to the controller 121. An external storage device 123 can also be connected to the controller 121. Furthermore, the substrate processing apparatus 100 can be configured to have one control unit or multiple control units. That is, control of the processing sequence described later can be performed using one control unit or multiple control units. Furthermore, multiple control units can be configured as a control system interconnected via a wired or wireless communication network, or the control system as a whole can perform control of the processing sequence described later. In this specification, the term "control unit" is used not only in cases involving a single control unit, but also in cases involving multiple control units, and in cases involving a control system composed of multiple control units.

[0053] The storage device 121c is configured such as flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), etc. The storage device 121c records and stores, in a readable manner, a control program that controls the operation of the substrate processing apparatus 100, and a process recipe that describes the steps and conditions of the substrate processing described later. The process recipe is a combination of components that enable the substrate processing apparatus 100 to execute each step of the substrate processing described later using the controller 121 and obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, control program, etc., will be collectively referred to as a program (program article). Furthermore, the process recipe will be simply referred to as a recipe. The term "program" may be used in this specification only in cases where only the recipe unit is included, only the control program unit is included, or both are included. The RAM 121b is configured as a storage area that temporarily holds the program, data, etc., read by the CPU 121a.

[0054] I / O port 121d is connected to the aforementioned MFC241a~241f, valves 243a~243f, pressure sensor 245, APC valve 244, vacuum pump 246, gate valves 10a and 10b, temperature sensors 263 and 620, heaters 207 and 630, conveying mechanism 750, etc.

[0055] CPU 121a is configured to read and execute control programs from storage device 121c, and to read recipes from storage device 121c based on input of operation instructions from input / output device 122. CPU 121a is configured to control, according to the read recipe, the following actions: flow rate adjustment of various substances (various gases) by MFCs 241a-241f; opening and closing of valves 243a-243e; opening and closing of APC valve 244 and pressure adjustment of APC valve 244 based on pressure sensor 245; starting and stopping of vacuum pump 246; temperature adjustment of heaters 207 and 630 based on temperature sensors 263 and 620; rotation and speed adjustment of crystal boat 217 by rotating mechanism 267; lifting and lowering of crystal boat 217 by crystal boat elevator 115; and operation of conveying mechanism 750.

[0056] The controller 121 can be configured to install the aforementioned program, which is recorded and stored in the external storage device 123, onto a computer. The external storage device 123 includes, for example, a hard disk such as an HDD, an optical disk such as a CD, a USB flash drive, or a semiconductor memory such as an SSD. The storage device 121c and the external storage device 123 constitute a computer-readable recording medium. Hereinafter, they will also be collectively referred to as recording media. The term "recording medium" may be used in this specification in cases where only the storage device 121c is included, in cases where only the external storage device 123 is included, or in cases where both are included. Furthermore, the program may be provided to the computer without using the external storage device 123, but instead using a communication mechanism such as the Internet or a dedicated line.

[0057] (2) Substrate processing process

[0058] The substrate processing apparatus 100 described above is used as a step in the manufacturing process of a semiconductor device, and mainly employs... Figure 7 (a) ~ Figure 7 (j) will describe a method for processing a substrate, namely, a processing sequence for forming a film on the surface of the wafer 200, which serves as the substrate. In the following description, the operation of each part constituting the substrate processing apparatus 100 is controlled by the controller 121.

[0059] In this embodiment, an example using a wafer 200 with recesses such as trenches, slots, and holes formed on its surface as three-dimensional structures will be described. Furthermore, in this embodiment, the region on the opening side and the region on the bottom side of the recesses are referred to as the first region and the second region, respectively (see reference). Figure 6 ).

[0060] Furthermore, in this specification, the term "recess" is not limited to shapes with a bottom surface; for example, it sometimes includes structures such as gaps (slits) or through holes that do not have a bottom surface. In the case of a structure that does not have a bottom surface, "bottom side" sometimes refers to the direction (side) from each opening toward the depth side of the structure when viewed from two or more openings.

[0061] In this method, steps A, B, C, and D, which will be described later, are performed in this order. Step A is performed in the film-forming apparatus 500, step B is performed in the removal apparatus 600, and steps C and D are performed in the film-forming apparatus 500.

[0062] In this specification, "selective removal" is not limited to a scheme that removes only one party while leaving the other party completely unremoved. It includes schemes where the amount, rate, or probability of removing one party is relatively greater than the amount, rate, or probability of removing the other party. In other words, it includes schemes where one party is removed with priority over the other.

[0063] Step A in this scheme is as follows: Prepare (provide) wafer 200, which includes a first film formed in a recess, and the surface of the first film in the recess is sealed by a first end capping that reduces the wettability to the processing solution (see reference). Figure 7 (b)

[0064] Furthermore, in this scheme, the cases where steps a1 and a2 are performed in step A will be explained. Step a1 involves supplying a raw material containing a predetermined element to the wafer 200 to form a first film containing the predetermined element within the recess (see reference). Figure 7 (a) Step a2 involves supplying a modifier to the wafer 200 in which the first film is formed within the recess, thereby modifying the surface of the first film to have a first end cap (see reference). Figure 7 (b)).

[0065] In addition, in this scheme, the case in which a first film is formed in the recess by performing the cycle including steps a1a and a1b a predetermined number of times (m1 times, where m1 is an integer of 1 or 2 or more) in step a1 is described, wherein step a1a is supplying raw materials to wafer 200 and step a1b is supplying a first reactant to wafer 200.

[0066] Furthermore, in this solution, the case where the recess is filled by the first film by performing a predetermined number of cycles (n1 times, where n1 is an integer of 1 or 2 or more) including steps B, C, and D after step A is described. In step B, a processing solution is supplied to the wafer 200, and the surface of the first film formed in the first region on the opening side of the recess is selectively exposed to the processing solution relative to the surface of the first film formed in the second region on the bottom side of the recess. This removes at least a portion of the first film formed in the first region while retaining residual first film in the second region (see reference). Figure 7 (c) Step C is after step B, feeding raw materials to wafer 200, thereby forming a first film in the recess after the first film formed in the first region has been removed (see reference). Figure 7 (e) Step D is, after step C, supplying a modifier to the wafer 200 in which the first film is formed in the recess, thereby modifying the surface of the first film to a surface having a first end cap (see reference). Figure 7 (f)).

[0067] In addition, in this scheme, a first film is formed in the recess by performing the cycle including steps c1 and c2 a predetermined number of times (m2 times, where m2 is an integer of 1 or 2 or more) in step C, wherein step c1 is to supply raw materials to wafer 200 and step c2 is to supply a first reactant to wafer 200.

[0068] Furthermore, in this scheme, step E is explained. Step E is performed after step B, where the wafer 200 undergoes heat treatment (annealing) to remove at least a portion of the first end cap from the surface of the first film (refer to...). Figure 7 (d)).

[0069] In this specification, for convenience, the above processing order is sometimes indicated as follows. The same expression is also used in the following descriptions of variations, other solutions, etc.

[0070] (Raw material → First reactant) × m1 → Modifier → [Processing liquid → Heat treatment → (Raw material → First reactant) × m2 → Modifier] × n1

[0071] The term "wafer" as used in this specification sometimes refers to the wafer itself, and sometimes to a laminate of the wafer and a predetermined layer or film formed on its surface. The term "surface of the wafer" as used in this specification sometimes refers to the surface of the wafer itself, and sometimes to the surface of a predetermined layer, etc., formed on the wafer. When described in this specification as "forming a predetermined layer on the wafer," it sometimes means forming the predetermined layer directly on the surface of the wafer itself, and sometimes it means forming the predetermined layer on a layer, etc., formed on the wafer. The term "substrate" as used in this specification is also synonymous with the term "wafer."

[0072] As used in this specification, the term "agent" includes at least one of gaseous and liquid substances. Liquid substances include mist substances. That is, film-forming agents (raw materials, reactants) and modifiers may each contain gaseous substances, liquid substances such as mist substances, or both.

[0073] As used in this specification, the term "layer" includes at least one of continuous layers and discontinuous layers. For example, the first to sixth layers and the oxide layer may include continuous layers, discontinuous layers, or both.

[0074] In this specification, when describing the adsorption or reaction of raw materials, reactants and modifiers relative to the surface of wafer 200, it includes not only the scheme in which they adsorb or react with the wafer surface while remaining in an undecomposed state, but also the scheme in which they decompose or intermediates generated by the detachment of their ligands adsorb or react with the surface of wafer 200.

[0075] (Wafer loading and crystal boat mounting)

[0076] When multiple wafers 200 are loaded into the crystal boat 217 via the conveyor mechanism 750, such as Figure 2 As shown, the crystal boat 217 supporting multiple wafers 200 is moved into the processing room 201 by the crystal boat elevator 115 (crystal boat carrying).

[0077] (Pressure and temperature adjustment)

[0078] After the wafer boat is loaded, vacuum pump 246 is used to exhaust the vacuum (reduced pressure exhaust) to bring the pressure (vacuum level) inside the processing chamber 201, i.e., the space where the wafer 200 exists, to the desired level. Additionally, heater 207 is used to heat the wafer 200 inside the processing chamber 201 to the desired processing temperature. Furthermore, rotation of the wafer 200 is initiated based on rotation mechanism 267. Additionally, heater 630 is controlled based on temperature information detected by temperature sensor 620 to bring the processing solution inside the processing tank 610 to the desired temperature. Exhausting the vacuum in the processing chamber 201, heating and rotating the wafer 200, and adjusting the temperature of the processing solution are all continuously performed at least until the processing of the wafer 200 is completed.

[0079] Then, execute steps A, B, E, C, and D in sequence. Furthermore, in step A, execute steps a1 and a2 in sequence.

[0080] [Step A: Preparation Process]

[0081] (Step a1: Film formation process)

[0082] In this step, a raw material containing predetermined elements and a first reactant are supplied to wafer 200. This forms a first film containing predetermined elements within the recess. Specifically, steps a1a and a1b are performed sequentially in this step.

[0083] [Step a1a]

[0084] In this step, a raw material containing predetermined elements is supplied to the wafer 200 within the processing chamber 201. Specifically, valve 243a is opened, allowing the raw material to flow into the gas supply pipe 232a. The flow rate of the raw material is adjusted by MFC 241a, supplied to the processing chamber 201 via nozzle 249a, and discharged from exhaust port 231a. At this time, the raw material is supplied to the wafer 200. Alternatively, valves 243d to 243f can be opened to supply inactive gases into the processing chamber 201 via nozzles 249a to 249c. Furthermore, the raw material used in this step is sometimes specifically referred to as the first raw material, and the raw material supply system for supplying the first raw material to the wafer 200 is specifically referred to as the first raw material supply system.

[0085] Examples of processing conditions for supplying raw materials in this step are as follows:

[0086] Processing temperature (first temperature): room temperature ~ 600℃, preferably 50℃ ~ 400℃;

[0087] Processing pressure: 1~101325Pa, preferably 1~1300Pa;

[0088] Raw material supply flow rate: 0.001~2 slm, preferably 0.001~1 slm;

[0089] Raw material supply time: 1 second to 240 minutes, preferably 30 seconds to 120 minutes;

[0090] Inactive gas supply flow rate (per gas supply pipe): 0~20slm.

[0091] Furthermore, the numerical ranges expressed in this specification, such as "50℃~400℃," refer to the inclusion of both the lower and upper limits within that range. Therefore, for example, "50℃~400℃" means "above 50℃ and below 400℃." The same applies to other numerical ranges. Additionally, the processing temperature in this specification refers to the temperature of the wafer 200 or the temperature within the processing chamber 201, and the processing pressure refers to the pressure within the processing chamber 201; in other words, the pressure of the space where the wafer 200 exists. Furthermore, the processing time refers to the duration of the processing. Also, when the supply flow rate includes 0 slm, 0 slm means that the substance is not supplied. These also apply to the following descriptions.

[0092] By supplying raw materials to wafer 200 under the above processing conditions, at least a portion of the molecular structure of the molecules constituting the raw materials can be adsorbed onto the first region and the second region, forming a first layer in these regions.

[0093] As a raw material, for example, a Si-containing material containing silicon (Si), which is the main element constituting the first film formed in step a1, can be used. As a Si-containing material, for example, a substance containing halogens and Si, i.e., a halosilane, can be used. Halogens include chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. As a halosilane, for example, chlorosilanes, fluorosilanes, bromosilanes, iodosilanes, etc., can be used.

[0094] As raw materials, chlorosilanes such as monochlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), tetrachlorosilane (SiCl4), hexachloroethylsilane (Si2Cl6), and octachloropropane (Si3Cl8) can be used.

[0095] In addition to these, substances containing amino groups and Si, namely aminosilanes, can also be used as raw materials.

[0096] As raw materials, aminosilanes such as tetra(dimethylamino)silane (Si[N(CH3)2]4), tri(dimethylamino)silane, bis(diethylamino)silane (Si[N(C2H5)2]2H2), bis(tert-butylamino)silane (SiH2[NH(C4H9)]2), and (diisopropylamino)silane (SiH3[N(C3H7)2]) can also be used.

[0097] As raw materials, one or more of them can be used.

[0098] As inert gases, rare gases such as nitrogen (N2), argon (Ar), helium (He), neon (Ne), and xenon (Xe) can be used. More than one of these gases can be used as an inert gas. This also applies to the steps described later.

[0099] After the first layer is formed in the first and second regions of wafer 200, valve 243a is closed to stop the supply of raw materials to processing chamber 201. Then, vacuum exhaust is performed in processing chamber 201 to remove any gaseous substances remaining there. At this time, valves 243d-243f are opened, and inactive gas is supplied to processing chamber 201 through nozzles 249a-249c. This inactive gas acts as a purge gas, thereby purging the space containing wafer 200, i.e., processing chamber 201.

[0100] [Step a1b]

[0101] After step a1a is completed, the first reactant is supplied to the wafer 200 in the processing chamber 201, that is, the wafer 200 after the first layer is formed in the first region and the second region.

[0102] Specifically, valve 243b is opened, allowing the first reactant to flow into gas supply pipe 232b. The first reactant, with its flow rate regulated by MFC 241b, is supplied to processing chamber 201 via nozzle 249b and discharged from exhaust port 231a. At this time, the first reactant is supplied to wafer 200.

[0103] Examples of processing conditions for supplying the first reactant in this step are as follows:

[0104] The first reactant supply flow rate is 0.001~20 slm, preferably 0.001~10 slm;

[0105] The first reaction body supply time is 1 second to 240 minutes, preferably 30 seconds to 120 minutes.

[0106] Other processing conditions can be set to be the same as those when supplying raw materials in step a1a.

[0107] By supplying a first reactant to wafer 200 under the aforementioned processing conditions, at least a portion of the first layer formed in the first and second regions can be modified. For example, when an oxygen-containing (O) substance is used as the first reactant, a second layer is formed in the first and second regions by oxidizing the first layer to form OH groups (hydroxyl groups) (OH-terminated).

[0108] As the first reactant, the aforementioned O-containing substances can be used, for example. Examples of O-containing substances include oxygen (O2), ozone (O3), nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), carbon monoxide (CO), and carbon dioxide (CO2). One or more of these can be used as the first reactant.

[0109] Furthermore, substances containing O and H can be used as the first reactant, for example. Gases containing O and H can include, for example, water vapor (H₂O), hydrogen peroxide (H₂O₂), mixtures of H₂ and O₂, mixtures of H₂ and O₃, etc. That is, mixtures of O-containing and H-containing substances can also be used as substances containing O and H. In this case, a deuterium-containing (D) substance can be used instead of an H-containing substance. Deuterium gas (D₂) can also be used as a D-containing substance. One or more of these can be used as the first reactant.

[0110] After the first layer formed in the first and second regions of the wafer 200 is changed to the second layer, valve 243b is closed to stop the supply of the first reactant into the processing chamber 201. Then, gaseous substances and the like remaining in the processing chamber 201 are removed from the processing chamber 201 by the same processing steps and conditions as in step a1a.

[0111] (Number of times to be implemented)

[0112] By performing steps a1a and a1b in this order m1 times (m1 being an integer of 1 or 2 or more), the first film can be formed in the first and second regions of the wafer 200. The first film formed in the recess of the wafer 200 can form an inner space of the recess that communicates with the outer space of the recess. For example, when using the above-mentioned raw materials and the first reactant, a SiO film, for example, can be formed as the first film in the first and second regions. Thus, a first film having a surface with OH end caps, for example, is formed in the first and second regions (see reference). Figure 7 (a)). The OH-terminals formed on the surface of the first membrane function as adsorption sites for the modifier supplied in step a2 described later. That is, the first membrane with OH-terminals functions as an adsorption-promoting membrane for the modifier. The above-described cycle is preferably repeated multiple times until the thickness of the first membrane formed by stacking the second layer becomes the desired thickness.

[0113] (Step a2: Modification process)

[0114] After step a1b, a modifier is supplied to the wafer 200 in the processing chamber 201, i.e., the wafer 200 after the first film has been formed in the first and second regions. Specifically, valve 243c is opened, allowing a gaseous modifier to flow into the gas supply pipe 232c. The modifier is regulated by MFC 241c, supplied to the processing chamber 201 via nozzle 249c, and discharged from exhaust port 231a. At this time, the modifier is supplied to the wafer 200. Alternatively, valves 243d to 243f can be opened to supply inactive gases into the processing chamber 201 via nozzles 249a to 249c. Furthermore, the modifier used in this step is sometimes specifically referred to as the first modifier, and the modifier supply system for supplying the first modifier to the wafer 200 is specifically referred to as the first modifier supply system.

[0115] Examples of processing conditions for supplying the modifier in this step are as follows:

[0116] Processing temperature: 25℃~500℃, preferably 50℃~300℃;

[0117] Processing pressure: 1~13300Pa, preferably 50~1330Pa;

[0118] Modifier supply flow rate: 0.01~3 slm, preferably 0.5~1 slm;

[0119] Modifier supply time: 0.1 seconds to 120 minutes, preferably 30 seconds to 60 minutes.

[0120] Other processing conditions can be set to be the same as those when supplying raw materials in step a1a.

[0121] By supplying a modifier to wafer 200 under the aforementioned processing conditions, at least a portion of the molecular structure constituting the modifier molecule can be adsorbed onto the surface of the first film to form a third layer. Specifically, the OH terminator formed on the surface of the first film can react with the modifier, causing at least a portion of the molecular structure constituting the modifier molecule to adsorb onto the surface of the first film. Thus, the surface of the first film can be terminated using at least a portion of the molecular structure constituting the modifier molecule. Examples of at least a portion of the molecular structure constituting the modifier molecule include: residues containing bonds between atoms (e.g., Si) and hydrogen groups (H groups) adsorbed on the surface of the first film (e.g., Si-H) after the functional group (e.g., amino group) of the modifier molecule is removed by the reaction of the OH terminator; and residues formed by the bonding between atoms adsorbed on the surface of the first film and alkoxy groups after the functional group (e.g., Si-OR) is removed by the reaction of the OH terminator with the functional group of the modifier molecule. When these residues are used for end-capping, H-terminals and alkoxy-terminals are formed on the surface of the first membrane as the first end-capping (see reference). Figure 7 (b) Figure 7 (Example shown in (b) is an example of forming an H-terminal as the first terminator). Alkoxy terminators include methoxy terminators, ethoxy terminators, propoxy terminators, butoxy terminators, etc. The first terminator formed on the surface of the first film is a terminator that reduces the wettability of the outermost surface of the wafer 200. By forming the first terminator on the surface of the first film, the wettability of the wafer 200 to the processing solution can be reduced in step B described later.

[0122] As modifiers, for example, tris(dimethylamino)silane (Si[N(CH3)2]3H), bis(diethylamino)silane (Si[N(C2H5)2]2H2), bis(tert-butylamino)silane (SiH2[NH(C4H9)]2), (diisopropylamino)silane (SiH3[N(C3H7)2]), (diisobutylamino)silane (SiH3[N(C4H9)2]), and (diisopentylamino)silane (SiH3[N(C5H5)2]) can be used. 11Compounds containing Si as a predetermined element, such as [2], and more specifically, substances having hydrogen (H) and an amino group bonded to Si, i.e., aminosilanes. Particularly preferred are substances such as (diisobutylamino)silane and (diisopropylamino)silane, which have three H atoms and one amino group bonded to Si, i.e., monoaminosilanes. By using monoaminosilanes as modifiers, in this step, the first end cap (H-end cap) can be formed more uniformly and sufficiently on the surface of the first film.

[0123] Furthermore, as a modifier, compounds containing Si as a predetermined element, such as (dimethylamino)trimethoxysilane (Si(OCH3)3[N(CH3)2]), (dimethylamino)triethoxysilane (Si(OC2H5)3[N(CH3)2]), (dimethylamino)tripropoxysilane (Si(OC3H7)3[N(CH3)2]), and (dimethylamino)tributoxysilane (Si(OC4H9)3[N(CH3)2]), can be used. More specifically, substances with alkoxy groups and amino groups bonded to Si are preferred. Substances with three alkoxy groups and one amino group bonded to Si are particularly preferred. By using such a substance as a modifier, in this step, the first end cap (alkoxy end cap) can be formed more uniformly and sufficiently on the surface of the first film.

[0124] As a modifier, one or more of them can be used.

[0125] (Post-purge and atmospheric pressure recovery)

[0126] After the first end caps are formed in the first and second regions of wafer 200, valve 243c is closed to stop the supply of modifier to processing chamber 201. Then, gaseous substances remaining in processing chamber 201 are removed from processing chamber 201 through the same processing steps and conditions as in step a1a. Afterward, the atmosphere in processing chamber 201 is replaced with an inactive gas, and the pressure in processing chamber 201 is restored to atmospheric pressure.

[0127] (Crystal boat unloading and wafer release)

[0128] Next, the sealing cap 219 is lowered by the crystal boat lift 115, opening the lower end of the manifold 209. Then, the wafer 200, supported on the crystal boat 217, is moved from the lower end of the manifold 209 to the outside of the reaction tube 203. After being moved to the outside of the reaction tube 203, the wafer 200 is removed from the crystal boat 217 by the conveying mechanism 750.

[0129] The wafer 200, taken out of the crystal boat 217 by the conveying mechanism 750, is placed in a loading stage (not shown) provided in the removal device 600 via the conveying chamber 700.

[0130] [Step B: Removal (Etching) Process]

[0131] In this step, a processing solution is supplied to the wafer 200 within the removal apparatus 600, specifically the wafer 200 on the surface of the first film where a first end cap has been formed. More specifically, the wafer 200 is exposed to a processing solution supplied via the processing solution supply pipe 640 and stored in the processing tank 610. More specifically, a moving mechanism (not shown) provided within the removal apparatus 600 immerses the wafer 200, placed on a stage within the removal apparatus 600, in the processing solution stored in the processing tank 610.

[0132] Examples of processing conditions for supplying the processing solution (i.e., exposure to the processing solution) in this step are as follows:

[0133] Exposure temperature: 0℃~100℃, preferably 15℃~50℃;

[0134] Exposure time: 0.1 seconds to 120 minutes, preferably 0.5 seconds to 60 minutes.

[0135] Furthermore, as will be described later, the processing conditions in this step can vary in each cycle as the bottom-up film formation proceeds.

[0136] Furthermore, the exposure temperature in this specification refers to the temperature of the wafer 200 in the processing solution or the temperature of the processing solution. Exposure time refers to the duration of continuous exposure, specifically the supply time of the processing solution. These terms also apply in the following descriptions.

[0137] By supplying a processing solution to the wafer 200 under the aforementioned processing conditions, the surface of the first film formed in the first region can be selectively exposed to the processing solution relative to the surface of the first film formed in the second region. In other words, at least a portion of the first film facing the inner space within the recess, specifically, the first film formed in the second region of the first film formed in both the first and second regions, can be left unexposed to the processing solution. Therefore, at least a portion of the first film facing the inner space within the recess can be left unremoved, specifically, the first film formed in the second region can be left unremoved. That is, at least a portion of the first film formed in the first region can be removed while retaining the residual first film formed in the second region (see reference). Figure 7 (c)).

[0138] As described above, the first end cap formed on the surface of the first film is an end cap that reduces the wettability of the outermost surface of the wafer 200. When the processing solution is an aqueous solution, it is an end cap that imparts hydrophobicity (water resistance) to the outermost surface of the wafer 200. The contact angle of the processing solution with respect to the first film having the first end cap on its surface is preferably 70° to 95°. Furthermore, the wettability of the first film having the first end cap on its surface is preferably such that the processing solution cannot penetrate into the inner side of the recess at the start of this step (i.e., the processing solution cannot substantially contact the sidewalls within the recess, including a state where a portion of the processing solution extends into the recess without contacting the sidewalls). In this case, the processing solution only reaches (contacts) the first film near the opening of the recess at the start of this step, and the first film near the opening is removed. Moreover, in this specification, the term "cannot penetrate" refers to the situation where the processing solution cannot substantially contact the sidewalls within the recess, including a state where a portion of the processing solution extends into the recess without contacting the sidewalls.

[0139] Furthermore, during this step, the first film is removed starting from the opening side as time passes. Thus, the first end cap and the first film are removed sequentially from the opening side, and the opening width of the recess expands, thereby increasing the area where the processing liquid can penetrate from the opening side of the recess towards the bottom side. Moreover, in this solution, exposure to the processing liquid continues until the processing liquid reaches (penetrates) the entire first region (the opening side of the recess), and at least a portion of the first film formed in the first region is removed; exposure to the processing liquid is stopped before the processing liquid reaches the second region (the bottom side of the recess). Therefore, the first film formed in the first region can be selectively removed relative to the first film formed in the second region (see reference). Figure 7 (c)).

[0140] In this step, it is preferable to control the extent of the surface of the first film exposed to the processing solution by adjusting the supply time (exposure time) of the processing solution to the wafer 200. For example, it is preferable to shorten the supply time of the processing solution when exposing the first film near an opening in the first film formed in the first region to the processing solution, and to extend the supply time of the processing solution when exposing the first film adjacent to the second region to the processing solution. Furthermore, Figure 7 (c) illustrates an example where the supply of the processing solution (exposure) in this step continues until the entire surface of the wafer 200 of the first region is exposed. However, the supply of the processing solution in this step may also be stopped before the entire surface of the wafer 200 of the first region is exposed, or before the surface of at least a portion of the wafer 200 of the first region is exposed. In this step, at least a portion of the first film formed in the first region is removed by widening the opening width of the recess.

[0141] Hydrofluoric acid (HF) aqueous solution can be used as the treatment liquid. By using an aqueous solution such as HF aqueous solution as the treatment liquid, OH end caps can be formed on the surface inside the recess in contact with the treatment liquid, and the density of the OH end caps can be adjusted (for example, by increasing the density of the OH end caps).

[0142] After selectively removing the first film formed in the first region, the wafer 200 is lifted from the processing tank 610 by a moving mechanism and placed on a mounting stage within the removal apparatus 600. The wafer 200 placed on the mounting stage is moved out of the removal apparatus 600 by a conveying mechanism 750 and loaded into the wafer boat 217 via a conveying chamber 700.

[0143] (Wafer loading and crystal boat mounting)

[0144] Then, following the same steps as the wafer loading and crystal boat mounting described above, the wafer 200 is loaded into the crystal boat 217 and moved into the processing chamber 201.

[0145] (Pressure and temperature adjustment)

[0146] Then, the pressure and temperature inside the processing chamber 201 are adjusted using the same steps as the pressure and temperature adjustments described above. At this time, step E, which will be described later, is prepared, by adjusting the output of the heater 207 to raise the temperature inside the processing chamber 201 from a first temperature to a second temperature that is higher than the first temperature.

[0147] [Step E: Heat treatment (annealing) process]

[0148] After the temperature in the processing chamber 201 stabilizes at the second temperature, the wafer 200 that has been moved from the removal device 600 into the processing chamber 201 of the film forming device 500, i.e. the wafer 200 after the first film formed in the first region has been selectively removed, is subjected to heat treatment (annealing).

[0149] Examples of processing conditions for heat treatment in this step are as follows:

[0150] Processing temperature (second temperature): 400~700℃, preferably 450~600℃;

[0151] Processing pressure: 500~101325Pa, preferably 800~10133Pa;

[0152] Processing time: 30 minutes to 120 minutes, preferably 30 minutes to 60 minutes.

[0153] By heat-treating the wafer 200 under the above-described processing conditions, the first end capping that remains on the surface of the first film in the second region can be removed (caused by detachment) (see reference). Figure 7(d) Thus, in this step, the first capping, which acts as an inhibitor preventing the raw material from adsorbing onto the surface of wafer 200 in step B described later, can be removed, resulting in a state where the raw material can easily adsorb onto the surface of wafer 200.

[0154] Next, the output of heater 207 is adjusted to lower the processing temperature from the second temperature to the first temperature. At this time, the processing chamber 201 is purged using the same processing steps and conditions as in step a1a.

[0155] [Step C: Film Formation Process]

[0156] In this step, a raw material containing predetermined elements and a first reactant are supplied to the wafer 200 within the processing chamber 201. As a result, a first film is formed within the recess after the first film formed in the first region is removed; more specifically, on the surface of the recess after the first film formed in the first region is removed. Specifically, in this step, steps c1 and c2 are performed sequentially. Furthermore, the "surface of the recess after the first film is removed" in this step is not limited to the surface of the wafer 200 exposed by removing the first film in step B; for example, in this embodiment, such as... Figure 7 As shown in example (d), it also includes the surface of the first membrane remaining in the second region.

[0157] [Step c1]

[0158] After the temperature inside the processing chamber 201 drops to the first temperature and stabilizes, raw materials are supplied to the wafer 200. In this step, the wafer 200 can be supplied with raw materials using the same processing steps and conditions as in step a1a. Sometimes, the raw materials used in this step are specifically referred to as the second raw material.

[0159] By supplying raw materials to wafer 200 under the above processing conditions, at least a portion of the molecular structure of the molecules constituting the raw materials can be adsorbed onto the surface of the recess after the first film formed in the first region is removed, thereby forming a fourth layer in the first and second regions.

[0160] Furthermore, as the raw material (second raw material) supplied to the wafer 200 in this step, one or more gases can be used, including those exemplified as the raw material (first raw material) supplied to the wafer 200 in step a1a. The second raw material may be the same as or different from the first raw material. When a raw material different from the first raw material is used as the second raw material, a second raw material supply system configured to supply the second raw material is also provided. The second raw material supply system is similar to the raw material supply system described above, and for example, consists of a gas supply pipe connected to the nozzle 249a, an MFC, and a valve.

[0161] After the fourth layer is formed in the first and second regions of wafer 200, valve 243a is closed to stop the supply of raw materials to processing chamber 201. Then, gaseous substances and the like remaining in processing chamber 201 are removed from processing chamber 201 by the same processing steps and conditions as in step a1a.

[0162] [Step c2]

[0163] After step c1 is completed, a first reactant is supplied to the wafer 200 in processing chamber 201, i.e., the wafer 200 after the fourth layer has been formed in the first and second regions. In this step, the first reactant can be supplied to the wafer 200 through the same processing steps and conditions as the first reactant in step a1b. Sometimes the reactant used in this step is specifically referred to as the fourth reactant.

[0164] By supplying the first reactant to the wafer 200 under the above-described processing conditions, at least a portion of the fourth layer formed in the first and second regions in step c1 can be modified. For example, when using an O-containing substance as the first reactant, a fifth layer is formed in the first and second regions by oxidizing the fourth layer to form OH groups (OH-terminated).

[0165] Furthermore, as the first reactant (fourth reactant) supplied to the wafer 200 in this step, one or more gases can be used, including those listed as examples of the first reactant supplied to the wafer 200 in step a1b. The fourth reactant may be the same as or different from the first reactant. When a reactant different from the first reactant is used as the fourth reactant, a fourth reactant supply system configured to supply the fourth reactant is also provided. The fourth reactant supply system is similar to the first reactant supply system described above, and for example, consists of a gas supply pipe connected to the nozzle 249b, an MFC, and a valve.

[0166] After changing the fourth layer formed in the first and second regions of wafer 200 to the fifth layer, valve 243b is closed to stop the supply of the first reactant into processing chamber 201. Then, gaseous substances and the like remaining in processing chamber 201 are removed from processing chamber 201 by the same processing steps and conditions as in step a1a.

[0167] (Number of times to be implemented)

[0168] By performing steps c1 and c2 in this order, which are not simultaneous, m2 times (m2 being an integer of 1 or 2), a new first film can be formed on the surface of the recess after the first film in the first region has been removed. Specifically, a new first film can be formed on the wafer 200 after the first film has been removed in step B in the first region, and a new first film can be formed on the first film that was not removed in step B and remains in the second region (see reference). Figure 7 (e)). Using the aforementioned raw materials and the first reactant, a first membrane, such as a SiO film, can be formed in the first and second regions. Thus, a first membrane having a surface with, for example, OH-terminated ends can be formed in the first and second regions (see [reference]). Figure 7 (e)). Preferably, the above cycle is repeated multiple times until the thickness of the first film formed by stacking the fifth layer becomes the desired thickness.

[0169] [Step D: Modification Process]

[0170] After step C is completed, a modifier is supplied to the wafer 200 in processing chamber 201, that is, the wafer 200 after a new first film is formed in the recess in step C. In this step, the modifier can be supplied to the wafer 200 using the same processing steps and conditions as in step a2. Sometimes the modifier used in this step is specifically referred to as the second modifier.

[0171] By supplying a modifier to wafer 200 under the aforementioned processing conditions, at least a portion of the molecular structure constituting the modifier molecules can be adsorbed onto the surface of the first film to form a sixth layer. Specifically, the OH termini formed on the surface of the first film can react with the modifier, causing at least a portion of the molecular structure constituting the modifier molecules to adsorb onto the surface of the first film. Thus, at least a portion of the molecular structure constituting the modifier molecules can be used to terminate the surface of the first film (first terminator formation, see [reference]). Figure 7 (f)). Examples and characteristics of the first end cap are as described in step a2.

[0172] Furthermore, as the modifier (second modifier) ​​supplied to wafer 200 in this step, one or more gases, including those exemplified as the modifier (first modifier) ​​supplied to wafer 200 in step a2, can be used. The second modifier may be the same as or different from the first modifier. When using a modifier different from the first modifier as the second modifier, a second modifier supply system configured to supply the second modifier is further provided. The second modifier supply system, like the modifier supply system described above, is, for example, composed of a gas supply pipe connected to nozzle 249c, an MFC, and a valve.

[0173] After the first end caps are formed in the first and second regions of wafer 200, valve 243c is closed to stop the supply of modifier to the processing chamber 201. Then, gaseous substances and the like remaining in the processing chamber 201 are removed from the processing chamber 201 by the same processing steps and conditions as in step a1a.

[0174] (Number of times to be implemented)

[0175] By performing steps B, E, C, and D in this order n1 times (n1 being an integer of 1 or 2), the first membrane can be grown from bottom to top, moving from the bottom side of the recess towards the opening side, thus filling the recess with the first membrane (see [reference]). Figure 7 (c)~ Figure 7 Specifically, by performing the cycle including steps C and B a predetermined number of times, a first film can be grown from the bottom side of the inner surface of the recess toward the opening side. Step C involves forming the first film in both the first and second regions, and step B involves selectively removing the first film formed in the first region relative to the first film formed in the second region. Preferably, the cycle is repeated multiple times until the recess is filled with the first film.

[0176] Furthermore, the extent of the first and second regions in each of the aforementioned steps B, E, C, and D cycles may differ in each cycle. For example, the supply (exposure) conditions of the processing liquid in step B can be set such that the first region in the k-th cycle (i.e., the region where the first film exposed to the processing liquid in step B of the k-th cycle is formed) is narrower from the opening of the recess compared to the first region in the (k-1)-th cycle (i.e., the region where the first film exposed to the processing liquid in step B of the (k-1)-th cycle is formed). Alternatively, for example, the supply conditions of the processing liquid in step B can be set such that the first region in the k-th cycle is the same as the first region in the (k-1)-th cycle.

[0177] Furthermore, preferably, during the above-described cycle, as film formation proceeds from bottom to top, adjustments are made in step B such as gradually shortening the supply (exposure) time of the processing solution to the wafer 200 and reducing the area of ​​the first film exposed to the processing solution surface. This allows for the formation of a void-free and seamless first film within the recess, improving the packing characteristics.

[0178] Then, the following steps are performed sequentially: post-purge, atmospheric pressure recovery, crystal boat unloading, and wafer release. The details are the same as those performed after step a2.

[0179] (3) The effect of this plan

[0180] According to this solution, one or more of the following effects can be achieved.

[0181] (a) In step A, a wafer 200 with a first end cap that reduces the wettability of the processing liquid is prepared to seal the surface of the first film. This makes it difficult for the processing liquid to penetrate into the inner side of the recess (especially the second region) in step B. Specifically, in step B, even if a wafer 200 with a relatively wide opening width w, in other words, where the processing liquid can more easily penetrate into the inner side of the recess (especially the second region), is used, the first end cap makes it difficult for the processing liquid to penetrate into the interior of the recess. As a result, in step B, the surface of the first film formed in the first region can be selectively exposed to the processing liquid relative to the surface of the first film formed in the second region. Consequently, at least a portion of the first film formed in the first region can be removed while retaining the first film formed in the second region. Thus, the first film formed in the first region can be selectively removed.

[0182] (b) In step B, the extent of the surface of the first film exposed to the processing solution is controlled by adjusting the timing of supplying the processing solution to the wafer 200. This allows for reliable selective removal of the first film formed in the first region relative to the first film formed in the second region. Furthermore, it allows for selective removal of the first film formed in the desired region from the first film formed in the first region, in conjunction with the bottom-up growth of the first film. As a result, a void-free and seamless first film can be formed within the recess.

[0183] (c) In step B, at least a portion of the first film facing the inner space of the recess, for example, the first film formed in the second region, is not exposed to the processing liquid. Thus, the first film formed in the first region can be reliably and selectively removed relative to the first film formed in the second region.

[0184] (d) In step B, at least a portion of the first membrane facing the inner space of the recess, for example, the first membrane formed in the second region, is not removed. Thus, bottom-up growth of the first membrane can be reliably performed.

[0185] (e) The wettability of the first sealing end is relative to the opening width of the recess at the start of step B, and the size at which the processing liquid cannot penetrate the inner side of the recess. Therefore, in step B, the processing liquid can reach the first region (the opening side of the recess) but has difficulty reaching (penetrating) the second region (the bottom side of the recess). Thus, the first film formed in the first region can be selectively removed relative to the first film formed in the second region.

[0186] (f) In step a2, a gaseous modifier is supplied to wafer 200, thereby enabling the modifier to be distributed not only throughout the first region but also throughout the second region. Thus, the aforementioned effects can be reliably obtained.

[0187] (g) After step C, step D is performed, which modifies the surface of the first film to have a first end cap by supplying a modifier to the wafer 200 in which the first film is formed in the recess. Thus, in step B of the next cycle, the first film formed in the first region can be reliably removed selectively relative to the first film formed in the second region.

[0188] (h) By repeatedly performing the cycle including steps B, C, and D, bottom-up film formation can be reliably achieved, thereby enabling gap-free filling.

[0189] (i) After step B, step E is performed to remove at least a portion of the first end cap from the surface of the first membrane. As a result, the first end cap, which acts as an inhibitor of the raw material, is removed, and thus in step C, the first membrane can be reliably formed not only in the first region but also in the second region.

[0190] (4) Variations

[0191] The substrate processing sequence in this scheme can be changed as shown in the following variations. These variations can be combined arbitrarily. Unless otherwise specified, the processing steps and conditions in each step of each variation can be the same as the processing steps and conditions in each step of the above processing sequence.

[0192] (Variation Example 1)

[0193] In the above-described scheme, an example of forming a first film (SiO film) on wafer 200 with adsorption sites (OH-terminated) for at least a portion of the molecular structure of the modifier (hereinafter also simply referred to as the modifier) ​​in steps A (specifically step a1) and C is described. Furthermore, an example of adsorbing the modifier onto these adsorption sites in steps A (specifically step a2) and D is described. However, for example, a first film (e.g., a SiN film) without adsorption sites (OH-terminated) for the modifier may be formed on wafer 200 in steps A (specifically step a1) and C. Moreover, in this case, an oxide layer with adsorption sites (OH-terminated) for the modifier may be formed on the surface of the first film in steps A (specifically step a2) and D, and the first terminator may be formed on the surface of the first film via this oxide layer. In this modified example, reference is mainly made to... Figure 8 (a) ~ Figure 8 (c) will be explained further. Figure 8 (a) ~ Figure 8 (c) is a partial schematic diagram of wafer 200 when performing step A in this variant example, and partial schematic diagrams of wafer 200 when performing steps B, E, C and D are omitted.

[0194] Based on the above, in this modified example, steps A, C, and D can also be changed in the processing order shown below.

[0195] (Raw material → Second reactant) × m3 → Oxide layer formation → Modifier → [Processing solution → Heat treatment → (Raw material → Second reactant) × m4 → Oxide layer formation → Modifier] × n2

[0196] Specifically, in step A of this variation, in step a1, the cycle of step a1a, which includes supplying raw materials to wafer 200, and step a1b, which includes supplying the second reactant, is performed a predetermined number of times (m3 times, where m3 is an integer of 1 or 2 or more), to form a first film (e.g., a SiN film) on wafer 200 (see reference). Figure 8 (a)). Then, the oxide layer formation step of forming an oxide layer on the first film is performed (see (a)). Figure 8 (b)). Then, in step a2, a first capping is formed on the surface of the first film by supplying a modifier to the wafer 200 on which the oxide layer is formed (see (b)). Figure 8 (c)).

[0197] Furthermore, in steps C to D of this modified example, in step C, the cycle including step c1 of supplying raw materials to wafer 200 and step c2 of supplying the second reactant is performed a predetermined number of times (m4 times, where m4 is an integer of 1 or 2 or more) to form a first film on wafer 200. Afterwards, an oxide layer formation step is performed to form an oxide layer on the first film. Then, in step D, a first capping is formed on the surface of the first film by supplying a modifier to the wafer 200 on which the oxide layer has been formed.

[0198] In this modified example, the processing steps and conditions of step A can be set to be the same as those of step A in the above-described scheme, except that the substance supplied in step a1b is the second reactant and the oxide layer formation step is performed after step a1 and before step a2.

[0199] In this modified example, the processing steps and conditions of steps C to D are the same as those of steps C to D in the above-described scheme, except that the substance supplied in step c2 is the second reactant and the oxide layer formation step is performed after step C and before step D.

[0200] Furthermore, the raw materials used in steps A and C of this modification can be substances with the same molecular structure as the raw materials in steps A and C of the above-described scheme. Additionally, the modifiers used in steps A and D of this modification can be substances with the same molecular structure as the modifiers in steps A and D of the above-described scheme.

[0201] When a nitriding gas (nitriding agent) containing nitrogen (N) and hydrogen (H) is used as the second reactant, a SiN film, for example, can be formed on wafer 200 in steps A and C. Thus, for example, a first film having a surface with NH end caps can be formed in the first and second regions (see...). Figure 8 (a)).

[0202] As a second reactant, substances containing N and H as described above can be used, for example. Substances containing N and H, such as ammonia (NH3), diazoxide (N2H2), hydrazine (N2H4), N3H8, and other hydrogen nitride-based substances, can be used, for example. One or more of these can be used as a second reactant.

[0203] Furthermore, in steps A and C of this modified example, a SiN film is formed as the first film, and thus, the processing solution supplied to the wafer 200 in step B of this modified example is preferably a hot phosphoric acid aqueous solution or the like.

[0204] In this modified example, the same effect as the above-described solution can also be obtained. In this modified example, even if a first film without adsorption sites for the modifier is formed on the wafer 200, the surface of the first film can be indirectly sealed by the first sealing layer by forming an oxide layer (with adsorption sites for the modifier) ​​on the surface of the first film. As a result, the wettability of the surface of the first film to the processing liquid can be reduced.

[0205] Furthermore, two main methods can be cited for forming the oxide layer in the above-described oxide layer formation steps. Details of these methods will be explained in the following modified examples 1-1 and 1-2.

[0206] [Modification 1-1: Oxide layer formation steps]

[0207] In the oxide layer formation step of this modified example, an oxide layer containing the predetermined element can also be formed on the first film by supplying a raw material containing an O-containing gas and a predetermined element to the wafer 200 (see reference). Figure 8 (b) Specifically, an oxide layer can be formed on the first film by repeating the steps of supplying raw materials to the wafer 200 and supplying the first reactant to the wafer 200 a predetermined number of times (p1 times, where p1 is an integer of 1 or 2 or more).

[0208] The oxide layer formation step in this variation can be configured to have the same processing steps and conditions as step A (specifically steps a1a and a1b) in the above-described scheme. The raw materials and the first reactant used in the oxide layer formation step in this variation can be substances with the same molecular structure as the raw materials and the first reactant in steps a1a and a1b of the above-described scheme.

[0209] [Modification 1-2: Oxide layer formation steps]

[0210] In the oxide layer formation step of this modified example, an oxidant can be supplied to the wafer 200 on which the first film is formed, so that the surface of the first film is oxidized (see reference). Figure 8 (b) Specifically, an oxide layer can be formed on the surface of the first film by supplying an activated first reactant, i.e., a first reactant excited to a plasma state, to the wafer 200, thereby oxidizing a portion of the first film (plasma oxidation).

[0211] Furthermore, the first reactant can be excited into a plasma state using the aforementioned RPU270. Specifically, valve 243b is opened, allowing the first reactant to flow into the gas supply pipe 232b. The first reactant is flow-regulated by MFC241b, excited into a plasma state by RPU270, supplied to the processing chamber 201 via nozzle 249b, and exhausted from exhaust port 231a. At this time, the first reactant is supplied to wafer 200.

[0212] In this variation, the first reactant used in the oxide layer formation step can be a substance with the same molecular structure as the first reactant in step a1b of the above-described scheme.

[0213] (Variation Example 2)

[0214] The above-described scheme illustrates an example where a SiO film is formed on wafer 200 as a first film in steps A and C, and the first film is sealed with an H-terminal as a first end-cap. However, for example, a carbon (C) film may be formed on wafer 200 as a first film in steps A and C, and a C-terminal as a first end-cap may be formed on the surface of the first film. In this modified example, reference is mainly made to... Figure 9 of (a) Figure 9 (b) will be explained further. Figure 9 of (a) Figure 9 (b) is a partial schematic diagram of wafer 200 when performing steps A and B in this variant example, while the partial schematic diagram of wafer 200 when performing steps E, C, and D is omitted.

[0215] Based on the above, in this modified example, steps A, C, and D can be changed to the following processing order.

[0216] (Raw material → Third reactant → First reactant) × m5 → [Processing liquid → Heat treatment → (Raw material → Third reactant → First reactant) × m6] × n3

[0217] Specifically, in step A of this variation, step a1 includes a predetermined number of cycles (m5 times, where m5 is an integer of 1 or 2 or more) of the steps a1a (supplying raw materials to wafer 200), a third reactant, and a first reactant, to form a first film on wafer 200. In step A of this variation, step a2, which is performed in the above-described scheme, can be omitted.

[0218] In step C of this variation, the cycle of supplying raw materials to wafer 200 (step c1), supplying the third reactant, and supplying the first reactant (step c2) will be performed a predetermined number of times (m6 times, where m6 is an integer of 1 or 2 or more) to form a first film on wafer 200. In this variation, step D, which is performed after step C in the above-described scheme, can be omitted.

[0219] In this modified example, the processing steps and conditions of step A, except that in step a1, in addition to supplying raw materials to wafer 200, a third reactant is also supplied to the first reactant, and step a2 is not performed, can be set to be the same as the processing steps and conditions of step A in the above-described scheme.

[0220] In this modified example, step C, in addition to supplying raw materials and the first reactant to wafer 200, also supplies a third reactant. Otherwise, it can be set to be the same as the processing steps and conditions of step C in the above-described scheme.

[0221] Furthermore, the raw materials and the first reactant used in steps A and C of this modified example can be substances with the same molecular structure as the raw materials and the first reactant in steps A and C of the above-described scheme.

[0222] As a step in supplying the third reactant to the wafer 200, valve 243c is opened, allowing the third reactant to flow into gas supply pipe 232c. The flow rate of the third reactant is regulated by MFC 241c, supplied to processing chamber 201 via nozzle 249c, and discharged from exhaust port 231a. At this time, the third reactant is supplied to wafer 200.

[0223] By supplying a third reactant to the wafer 200 under the aforementioned processing conditions, at least a portion of a layer containing, for example, Si and O, formed on the wafer 200 by supplying raw materials and a first reactant can be modified. For example, when a C-containing substance is used as the third reactant, the layer containing, for example, Si and O, formed on the wafer 200 is carbonized to form a C-based (carbon-based) capped (C-capped) SiOC layer.

[0224] As a third reactant, the aforementioned carbon-containing substances can be used, for example. As carbon-containing substances, ethylene (C2H4), acetylene (C2H2), propylene (C3H6), etc., can be used, for example. One or more of these can be used as the third reactant.

[0225] By performing a cycle of supplying the aforementioned raw material, third reactant, and first reactant separately in this order, m6 times (m6 being an integer of 1 or 2), a first film can be formed on wafer 200. For example, using the aforementioned raw material, first reactant, and third reactant, a SiOC film, for example, can be formed on wafer 200 as the first film. The surface of the SiOC film is sealed by a C-terminal as a first end-capping. Therefore, when the first film is formed on wafer 200, simultaneously, a C-terminal as a first end-capping is formed on the surface of the first film, reducing the wettability to the processing liquid (see reference). Figure 9 (a)).

[0226] In this modified example, the same effect as the above-described solution can also be obtained. Furthermore, in this modified example, after the formation of the first film, the step of modifying the surface to have a first end cap can be skipped, and step B (removal process) can be performed (see...). Figure 9 of (a) Figure 9 (b)

[0227] <Other options disclosed herein>

[0228] The above details the proposed solution. However, this disclosure is not limited to the above-described solution and various modifications can be made without departing from its main purpose.

[0229] For example, as the modifier used in the modification process (step a2, step D), substances with amino and alkyl groups bonded to Si, such as (dimethylamino)trimethylsilane ((CH3)2NSi(CH3)3), (diethylamino)triethylsilane ((C2H5)2NSi(C2H5)3), (dimethylamino)triethylsilane ((CH3)2NSi(C2H5)3), (diethylamino)trimethylsilane ((C2H5)2NSi(CH3)3), and (diisopropylamino)trimethylsilane ((C3H7)2NSi(CH3)3), i.e., alkylaminosilanes, can be used. In this case, alkyl end-caps are formed on the surface of the first film as the first end-cap. In this solution, the same effect as the above-described solution can also be obtained.

[0230] Generally, as the first end-capping, forming an alkyl end-capping is more effective than forming an H-end or an alkoxy end-capping in increasing the force that reduces the wettability of the wafer 200 to the processing solution (i.e., it increases the hydrophobicity of the wafer 200 surface). Therefore, for example, when forming an alkyl end-capping as the first end-capping, the processing time in the removal process (step B) is longer than when forming an H-end or an alkoxy end-capping, but on the other hand, a more stable and controllable removal can be performed. These factors are preferably considered when selecting the modifier used.

[0231] In the above-described scheme, step B illustrates a method for controlling the range of the surface of the first film exposed to the processing solution by adjusting the time of supplying the processing solution to the wafer 200. However, for example, the modifier used can also be selected considering the degree of hydrophobicity of the modifier. Alternatively, the density of the first end caps (e.g., OH end caps) on the surface of the wafer 200, which serve as adsorption sites for the modifier, can be adjusted by supplying an oxidant or similar substance to the wafer 200 before supplying the modifier. In this case, the oxidant supply method allows the wafer 200 to be exposed to the atmosphere. The same effect as the above-described scheme can be obtained in this scheme.

[0232] In the above-described scheme, an example is given of heat treatment (annealing) of wafer 200 as a method to detach the first end cap from the surface of wafer 200 before performing the film deposition process (step C). However, for example, a liquid containing OH bonds, such as an oxidant or ethanol-water, with a surface tension lower than that of the treatment liquid, can also be supplied to wafer 200. Furthermore, when step C is performed at high temperatures, the first end cap may detach from the surface of wafer 200 during the execution of step C, thus sometimes pretreatment is unnecessary. In this scheme, the same effect as the above-described scheme can also be obtained.

[0233] In the above scheme, step D (modification step) illustrates the case where the same modifier is used in every cycle. However, for example, the hydrophobicity of the first end cap can be different in each cycle, such as using an aminosilane in the first cycle and an alkylaminosilane in the second cycle. Similarly, in the above scheme, step B (removal step) illustrates the case where the same treatment solution is used in every cycle. However, the surface tension of the treatment solution can be different in each cycle, such as using an aqueous HF solution in the first cycle and an aqueous HF solution with added alcohol in the second cycle. This allows control over the extent of the surface of the first film exposed to the treatment solution and the processing time.

[0234] The above scheme exemplifies the case where the predetermined element contained in the raw material is Si. However, the predetermined element can also be, for example, titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), niobium (Nb), aluminum (Al), molybdenum (Mo), tungsten (W), germanium (Ge), or other metallic elements. In these cases, an oxide film containing these metallic elements or a nitride film containing these metallic elements is formed as the first film. The same effect as the above scheme can be obtained in this scheme.

[0235] Furthermore, the processing solution used in step B preferably varies depending on the type of the first membrane. When the first membrane is, for example, an aluminum oxide film, a hafnium oxide film, or a titanium oxide film, an aqueous HF solution is preferably used as the processing solution. When the first membrane is, for example, a titanium nitride film, a mixture of ammonia, hydrogen peroxide solution, and pure water is preferably used as the processing solution. In this embodiment, the same effects as described above can be obtained.

[0236] Although not specifically described in the above scheme, the effects of the above scheme can be significantly obtained when the wafer 200 has an opening width w such that the processing liquid is difficult to penetrate into the inside of the recess due to the formation of a first end cap on the surface of the first film. Specifically, for example, the effects of the above scheme can be significantly obtained when the opening width w of the recess at the beginning of step B is such that the processing liquid cannot penetrate into the inside of the recess due to the surface tension of the processing liquid, or when the processing liquid can penetrate into the inside of the recess when there is no first end cap on the surface of the first film.

[0237] This disclosure is not limited to the methods described above. For example, it can also be appropriately applied when forming films using a monolithic substrate processing apparatus 100 that processes one or more substrates at a time. Furthermore, this disclosure is not limited to the above-described solutions; it can also be appropriately applied when forming films using a substrate processing apparatus 100 with a cold-wall type processing furnace. When using these substrate processing apparatuses 100, each processing step and processing condition can be performed with the same methods and modifications as described above, and the same effects as described above can be obtained.

[0238] The above-mentioned schemes and variations can be used in appropriate combinations. The processing steps and conditions can be set to be the same as those in the above-mentioned schemes and variations.

Claims

1. A substrate processing method characterized by, It includes the following processes: (a) Preparing a substrate, wherein the substrate includes a first film formed in a recess, and the surface of the first film in the recess is sealed by a first end cap that reduces wettability to a processing liquid; and (b) The processing liquid is supplied to the substrate, and the surface of the first film formed in the first region on the opening side of the recess is selectively exposed to the processing liquid relative to the surface of the first film formed in the second region on the bottom side of the recess, thereby removing at least a portion of the first film formed in the first region while retaining the first film remaining in the second region.

2. The substrate processing method according to claim 1, characterized in that, The first end cap is formed on the surface of the first film by supplying a modifier to the substrate in which the first film is formed in the recess.

3. The substrate processing method according to claim 1, characterized in that, The first capping is formed by at least a portion of the molecular structure of the modifier adsorbing onto adsorption sites of the oxide layer formed on the surface of the first film prior to the formation of the first capping.

4. The substrate processing method according to claim 1, characterized in that, The first membrane is a carbon-containing membrane, and the first end cap is an end cap composed of carbon contained in the first membrane.

5. The substrate processing method according to claim 1, characterized in that, In (b), the extent of the surface of the first film exposed to the processing liquid is controlled by adjusting the time of supplying the processing liquid to the substrate.

6. The substrate processing method according to claim 1, characterized in that, The first film formed in the recess of the substrate prepared in (a) forms an inner space of the recess that communicates with the outer space of the recess. In (b), at least a portion of the first membrane facing the inner space is not exposed to the treatment liquid.

7. The substrate processing method according to claim 1 or 6, characterized in that, The first film formed in the recess of the substrate prepared in (a) forms an inner space of the recess that communicates with the outer space of the recess. In (b), at least a portion of the first membrane facing the inner space is not removed.

8. The substrate processing method according to claim 1, characterized in that, (b) The width of the opening of the recess at the start of execution is the width at which the processing liquid cannot contact the inner sidewall of the recess.

9. The substrate processing method according to claim 1, characterized in that, (b) The width of the opening of the recess at the start of execution is the width by which the treatment liquid can penetrate into the inside of the recess when the first sealing end is not present on the surface of the first membrane.

10. The substrate processing method according to claim 9, characterized in that, The wettability is the degree to which the processing liquid cannot contact the inner sidewall of the recess at the start of execution of (b).

11. The substrate processing method according to claim 1, characterized in that, (a) Includes the following processes: (a-1) By supplying the substrate with a raw material containing a predetermined element, the first film containing the predetermined element is formed in the recess.

12. The substrate processing method according to claim 1 or 11, characterized in that, (a) Includes the following processes: (a-2) By supplying a modifier to the substrate in which the first film is formed in the recess, the surface of the first film is modified to have the first end cap.

13. The substrate processing method according to claim 12, characterized in that, In (a-2), the modifier in gaseous form is supplied to the substrate.

14. The substrate processing method according to claim 11, characterized in that, It also includes the following processes: (c) After (b), the raw material is supplied to the substrate, thereby forming the first film in the recess after the first film formed in the first region has been removed.

15. The substrate processing method according to claim 14, characterized in that, It also includes the following processes: (d) After (c), a modifier is supplied to the substrate in which the first film is formed in the recess, thereby modifying the surface of the first film to have the first end cap.

16. The substrate processing method according to claim 15, characterized in that, Execute the loop that includes (b), (c), and (d) multiple times.

17. The substrate processing method according to claim 1, characterized in that, It also includes the following processes: (e) After (b), at least a portion of the first end cap is removed from the surface of the first membrane.

18. A method of manufacturing a semiconductor device, characterized by It has the following processes: (a) Preparing a substrate, wherein the substrate includes a first film formed in a recess, and the surface of the first film in the recess is sealed by a first end cap that reduces wettability to a processing liquid; and (b) The processing liquid is supplied to the substrate, and the surface of the first film formed in the first region on the opening side of the recess is selectively exposed to the processing liquid relative to the surface of the first film formed in the second region on the bottom side of the recess, thereby removing at least a portion of the first film formed in the first region while retaining the first film remaining in the second region.

19. An article of manufacture, comprising: The following steps are performed by the substrate processing apparatus using a computer: (a) Preparing a substrate, wherein the substrate includes a first film formed in a recess, and the surface of the first film in the recess is sealed by a first end cap that reduces wettability to a processing liquid; and (b) The processing liquid is supplied to the substrate, and the surface of the first film formed in the first region on the opening side of the recess is selectively exposed to the processing liquid relative to the surface of the first film formed in the second region on the bottom side of the recess, thereby removing at least a portion of the first film formed in the first region while retaining the first film remaining in the second region.

20. A substrate processing apparatus, comprising: have: A processing liquid supply system that supplies processing liquid to a substrate; and The control unit is configured to control the processing liquid supply system to perform a process in which the processing liquid is supplied to a substrate containing a first film formed in a recess and the surface of the first film in the recess is sealed by a first end that reduces the wettability of the processing liquid. The surface of the first film formed in a first region on the opening side of the recess is selectively exposed to the processing liquid relative to the surface of the first film formed in a second region on the bottom side of the recess. At least a portion of the first film formed in the first region is removed while retaining the first film remaining in the second region.

21. The substrate processing apparatus according to claim 20, characterized in that, It also includes a modifier supply system for supplying modifiers to the substrate. The control unit is configured to control the modifier supply system to perform a process of modifying the surface of the first film to have the first end cap by supplying the modifier to the substrate in which the first film is formed in the recess.

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