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

Abstract

The invention relates to a substrate processing method, a method of manufacturing a semiconductor device, a program product, and a substrate processing apparatus. The present invention addresses the problem of providing a technique capable of selectively processing a desired region in the surface of a recess formed in a substrate. (a) a step for preparing a substrate having a first region, which constitutes the outer surface of a recess and which is adjacent to an opening of the recess, and a second region, which constitutes the inner surface of the recess, which is capped by a first end, which constitutes the outer surface of the recess and which is adjacent to the opening of the recess, and which is capped by the first end; and (b) a step in which the substrate is exposed to a first processing liquid containing a liquid that reacts with the first terminal, thereby removing the first terminal in the first region such that the density of the first terminal in the first region becomes smaller than the density of the first terminal in the second region.

Description

TECHNICAL FIELD

[0001] The present application relates to a substrate processing method, a manufacturing method of a semiconductor device, a program product, and a substrate processing apparatus. BACKGROUND

[0002] As one of manufacturing processes of a semiconductor device, a substrate having a recess formed on a surface is sometimes subjected to a prescribed process (see, for example, Patent Literature 1).

[0003] PRIOR ART DOCUMENT

[0004] PATENT LITERATURE

[0005] Patent Literature 1: Japanese Patent Application Laid-Open No. 2023-123717 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] The present application provides a technology capable of selectively processing a desired region in a surface of a recess formed in a substrate.

[0008] MEANS FOR SOLVING THE PROBLEMS

[0009] According to one embodiment of the present application, there is provided a technology including:

[0010] (a) a step of preparing a substrate having a first region capped with a first end, the first region constituting a surface outside of a recess and being adjacent to an opening of the recess, and a second region capped with the first end, the second region constituting an inner surface of the recess; and

[0011] (b) a step of removing the first end of the first region in such a manner that a density of the first end in the first region becomes smaller than a density of the first end in the second region, by exposing the substrate to a first processing liquid containing a liquid that reacts with the first end.

[0012] EFFECT OF THE INVENTION

[0013] According to the present application, a desired region in a surface of a recess formed in a substrate can be selectively processed. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 FIG. 1 is a schematic configuration diagram of a substrate processing apparatus 100 that can be suitably used in each of the embodiments of the present application.

[0015] Figure 2This is a schematic configuration diagram of the vertical processing furnace of the film deposition apparatus 500 included in the substrate processing apparatus 100 which can be suitably used in various embodiments of the present invention, and is a diagram showing the processing furnace 202 portion in a longitudinal cross-sectional view.

[0016] Figure 3 This is a schematic configuration diagram of a vertical processing furnace of a film deposition apparatus 500 included in a substrate processing apparatus 100 that can be suitably used in various embodiments of the present invention. Figure 2 The AA-line cross-sectional view shows part of the processing furnace 202.

[0017] Figure 4 This is a schematic configuration diagram of the first cleaning device 600 and the second cleaning device 700 included in the substrate processing apparatus 100 that can be suitably used in various embodiments of the present invention.

[0018] Figure 5 This is a schematic configuration diagram of the controller 121 of the substrate processing apparatus 100 that can be suitably used in various embodiments of the present invention, and is a block diagram showing the control system of the controller 121.

[0019] Figure 6 This is a diagram illustrating the regions of the inner and outer surfaces of the recesses provided on the surface of the wafer 200 in various embodiments of the present invention.

[0020] Figure 7 (a) in Figure 7 (d) is a cross-sectional schematic diagram showing the surface portion of the wafer 200 with a recess in the first embodiment of the present invention; Figure 7 (a) is a partial schematic diagram of the wafer 200 after step a0 has been performed; Figure 7 (b) in the middle is from Figure 7 The state in (a) is a partial schematic diagram of the wafer 200 after step a1 has been implemented; Figure 7 (c) in the middle is from Figure 7 The state in (b) is a partial schematic diagram of the wafer 200 after step B has been implemented; Figure 7 (d) in the middle is from Figure 7 The state in (c) is a partial schematic diagram of the wafer 200 after step C.

[0021] Figure 8 (a) in Figure 8 (d) is a cross-sectional schematic diagram showing the surface portion of the wafer 200 with a recess in a modified example 1 of the first aspect of the present invention; Figure 8 (a) is a partial schematic diagram of the wafer 200 after step a0 has been performed; Figure 8 (b) in the middle is from Figure 8 The state in (a) is a partial schematic diagram of the wafer 200 after step a1 has been implemented;Figure 7 (c) in the middle is from Figure 8 The state in (b) is a partial schematic diagram of the wafer 200 after step B has been implemented; Figure 8 (d) in the middle is from Figure 8 The state in (c) is a partial schematic diagram of the wafer 200 after step C.

[0022] Figure 9 (a) in Figure 9 (f) is a cross-sectional schematic diagram showing the surface portion of the wafer 200 with a recess in the second aspect of the present invention; Figure 9 (a) is a partial schematic diagram of the wafer 200 after step a0 has been performed; Figure 9 (b) in the middle is from Figure 9 The state in (a) is a partial schematic diagram of the wafer 200 after step a1 has been implemented; Figure 9 (c) in the middle is from Figure 9 The state in (b) is a partial schematic diagram of the wafer 200 after step B has been implemented; Figure 9 (d) in the middle is from Figure 9 The state (c) in the diagram represents a partial schematic of the wafer 200 after step D has been implemented; Figure 9 (e) in the middle is from Figure 9 The state (d) in the diagram represents a partial schematic of the wafer 200 after step E has been implemented; Figure 9 (f) in the middle is from Figure 10 The state (e) in the diagram represents a partial schematic of the wafer 200 after step F has been implemented.

[0023] Figure 10 (a) in Figure 10 (f) is a cross-sectional schematic diagram showing the surface portion of the wafer 200 with a recess in a modified example 1 of the second aspect of the present invention; Figure 10 (a) is a partial schematic diagram of the wafer 200 after step a0 has been performed; Figure 10 (b) in the middle is from Figure 10 The state in (a) is a partial schematic diagram of the wafer 200 after step a1 has been implemented; Figure 10 (c) in the middle is from Figure 10 The state in (b) is a partial schematic diagram of the wafer 200 after step B has been implemented; Figure 10 (d) in the middle is from Figure 10 The state (c) in the diagram represents a partial schematic of the wafer 200 after step D has been implemented; Figure 10 (e) in the middle is from Figure 10 The state (d) in the diagram represents a partial schematic of the wafer 200 after step E has been implemented;

[0024] Figure 10 (f) in the middle is fromFigure 1 The state (e) in the diagram represents a partial schematic of the wafer 200 after step F has been implemented.

[0025] Explanation of reference numerals in the attached figures

[0026] 200 wafers (substrates) Detailed Implementation

[0027] <First aspect of the present invention>

[0028] Hereinafter, a first aspect of the present invention will be described with reference to the accompanying drawings. It should be noted that the drawings used in the following description are schematic, and the dimensional relationships and ratios of the elements shown in the drawings may not necessarily correspond to reality. Furthermore, the dimensional relationships and ratios of the elements may not be consistent between different drawings.

[0029] (1) Configuration of substrate processing apparatus 100

[0030] like Figure 2 As shown, the substrate processing apparatus 100 mainly includes a film forming apparatus 500, a first cleaning apparatus 600, a second cleaning apparatus 700, and a transfer chamber 800.

[0031] The film deposition apparatus 500 is an apparatus for performing film deposition on the wafer 200 in the substrate processing steps described later. The first cleaning apparatus 600 and the second cleaning apparatus 700 are apparatuses for performing cleaning on the wafer 200 in the substrate processing steps described later. The transfer chamber 800 is the area where the wafer 200 is transferred between the film deposition apparatus 500 and the first cleaning apparatus 600 or between the film deposition apparatus 500 and the second cleaning apparatus 700.

[0032] (i) Composition of the film-forming apparatus 500

[0033] like Figure 3 As shown, the processing furnace 202 has a heater 207 as a temperature regulating unit (heating unit). The heater 207 is cylindrical and is vertically mounted by being supported by a retaining plate. The heater 207 also functions as an activation mechanism (activation unit) for activating (exciting) gas by heat.

[0034] On the inner side of the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is formed in a cylindrical shape with an upper end closed and a lower end open. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. An O-ring 220a is provided as a sealing member 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. In the cylindrical hollow portion of the processing container, a processing chamber 201 is formed. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed in the processing chamber 201.

[0035] In the processing chamber 201, nozzles 249a and 249b as a first supply portion and a second supply portion are provided, respectively, in a manner that penetrates the sidewall of the manifold 209. The nozzles 249a and 249b are also referred to as a first nozzle and a second nozzle, respectively. The nozzles 249a and 249b are configured as common nozzles for supply of a plurality of gases.

[0036] Gas supply pipes 232a and 232b as a first pipe and a second pipe are connected to the nozzles 249a and 249b, respectively. The gas supply pipes 232a and 232b are configured as common pipes for supply of a plurality of gases. On the gas supply pipes 232a and 232b, mass flow controllers (MFCs) 241a and 241b as flow controllers (flow control portions) and valves 243a and 243b as on-off valves are provided in this order from the upstream side of the gas flow, respectively. On the gas supply pipe 232a, gas supply pipes 232c and 232d are connected to the downstream side of the valve 243a, respectively. On the gas supply pipes 232c and 232d, MFCs 241c and 241d and valves 243c and 243d are provided in this order from the upstream side of the gas flow, respectively. On the gas supply pipe 232b, a gas supply pipe 232e is connected to the downstream side of the valve 243b. On the gas supply pipe 232e, an MFC 241e and a valve 243e are provided in this order from the upstream side of the gas flow.

[0037] As Figure 4As shown, the nozzles 249a, 249b are respectively provided in the space between the inner wall of the reaction tube 203 and the wafer 200 in a manner rising from the lower portion of the inner wall of the reaction tube 203 toward the upper portion above the arrangement direction of the wafer 200 toward the wafer 200. That is, the nozzles 249a, 249b are respectively provided in the area horizontally surrounding the wafer arrangement area along the side of the wafer arrangement area in which the wafer 200 is arranged. Gas supply holes 250a, 250b for supplying gas are respectively provided in the side surface of the nozzles 249a, 249b. The gas supply holes 250a, 250b respectively open toward the center of the wafer 200 in plan view and are capable of supplying gas toward the wafer 200. The gas supply holes 250a, 250b are provided in a plurality of stages from the lower portion to the upper portion of the reaction tube 203.

[0038] The raw material as the film forming agent is supplied from the gas supply pipe 232a to the inside of the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.

[0039] The oxidizing agent as the film forming agent is supplied from the gas supply pipe 232b to the inside of the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b. The oxidizing agent is one of the reactants as the film forming agent.

[0040] At least one of the first modifier and the second modifier is supplied from the gas supply pipe 232c to the inside of the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249a.

[0041] The non-active gas is supplied from the gas supply pipes 232d, 232e to the inside of the processing chamber 201 via the MFCs 241d, 241e, the valves 243d, 243e, the gas supply pipes 232a, 232b, and the nozzles 249a, 249b, respectively. The non-active gas functions as a purge gas, a carrier gas, a dilution gas, and the like.

[0042] The raw material supply system (may also be referred to as a raw material exposure system) is mainly constituted by the gas supply pipe 232a, the MFC 241a, and the valve 243a. The oxidizing agent supply system or the reactant supply system (may also be referred to as an oxidizing agent exposure system or a reactant exposure system) is mainly constituted by the gas supply pipe 232b, the MFC 241b, and the valve 243b. The modifier (the first and second modifiers) supply system (may also be referred to as a modifier exposure system) is mainly constituted by the gas supply pipe 232c, the MFC 241c, and the valve 243c. The non-active gas supply system is mainly constituted by the gas supply pipes 232d, 232e, the MFCs 241d, 241e, and the valves 243d, 243e. In addition, the raw material supply system and the oxidizing agent supply system can be collectively referred to as a film forming agent supply system (may also be referred to as a film forming agent exposure system). The nozzles connected to the gas supply pipes constituting the above-described various supply systems can be respectively included in the supply systems.

[0043] An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided below the side wall of the reaction tube 203. An exhaust pipe 231 is connected to the exhaust port 231a. On the exhaust pipe 231, a vacuum pump 246 as a vacuum exhaust device is connected via a pressure sensor 245 as a pressure detector (pressure detection section) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure regulation section). The APC valve 244 is configured to be able to perform vacuum exhaust and vacuum exhaust stop in the processing chamber 201 by opening and closing the valve in a state in which the vacuum pump 246 is operated, and to be able to regulate the pressure in the processing chamber 201 by regulating the valve opening degree based on the pressure information detected by the pressure sensor 245 in a state in which the vacuum pump 246 is operated. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 can also be included in the exhaust system.

[0044] A seal cap 219 as a furnace cap body capable of hermetically closing the lower end opening of the manifold 209 is provided below the manifold 209. An O-ring 220b as a sealing member is provided on the upper surface of the seal cap 219 so as to abut against the lower end of the manifold 209. A rotation mechanism 267 for rotating the wafer boat 217 described later is provided below the seal cap 219. A 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 as a lifting mechanism is configured as a conveyance device (conveyance mechanism) that conveys the wafer 200 into and out of the processing chamber 201 by lifting the seal cap 219.

[0045] A gate 219s as a furnace cap body capable of hermetically closing the lower end opening of the manifold 209 in a state in which the wafer boat 217 is conveyed out of the processing chamber 201 is provided below the manifold 209. An O-ring 220c as a sealing member is provided on the upper surface of the gate 219s so as to abut against the lower end of the manifold 209. The opening and closing operation of the gate 219s is controlled by a gate opening and closing mechanism 115s.

[0046] The wafer boat 217 as a substrate support is configured to support a plurality of, for example, 25 to 200 wafers 200 in a horizontal posture and in a state in which the wafers 200 are aligned with their centers and are arranged in multiple layers, that is, are arranged at intervals. The heat insulating plates 218 are supported in multiple layers in the lower portion of the wafer boat 217.

[0047] A temperature sensor 263, serving as a temperature detector, is installed inside the reaction tube 203. By adjusting the energization of the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature within the processing chamber 201 is adjusted to achieve the desired temperature distribution. The temperature sensor 263 is disposed along the inner wall of the reaction tube 203.

[0048] (ii) Composition of the first cleaning device 600

[0049] like Figure 4 As shown, the first cleaning apparatus 600 includes a processing tank 610. The processing tank 610 can accommodate 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 can supply processing liquid into the processing tank 610. The processing tank 610 stores the processing liquid for exposure, forming a system for immersing the wafers 200. The processing liquid supply pipe 640 and the LMFC 650 constitute a processing liquid exposure system (or a processing liquid supply system for supplying processing liquid to the wafers 200) that exposes the wafers 200 to the processing liquid. The processing liquid exposure system may also include the processing tank 610. The first cleaning 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 disposed near the processing tank 610 and maintains the processing liquid in the processing tank 610 at an appropriate temperature based on the temperature sensor 620.

[0050] (iii) Composition of the second cleaning device 700

[0051] like Figure 1 As shown, the second cleaning apparatus 700 includes a processing tank 710. The processing tank 710 can accommodate one or more wafers 200. A processing liquid supply pipe 740 is connected to a processing liquid tank (not shown) via an LMFC 750, configured to supply processing liquid into the processing tank 710. The processing tank 710 stores exposure processing liquid, forming a system for immersing the wafers 200. The processing liquid supply pipe 740 and the LMFC 750 constitute a processing liquid exposure system (processing liquid supply system) that exposes the wafers 200 to the processing liquid. The processing liquid exposure system may also include the processing tank 710. The second cleaning apparatus 700 includes a temperature sensor 720 for detecting the temperature of the processing liquid and a heater 730 for adjusting the temperature of the processing liquid. The temperature sensor 720 is disposed along the inner wall of the processing tank 710. The heater 730 is disposed near the processing tank 710 and maintains the processing liquid in the processing tank 710 at an appropriate temperature based on the temperature sensor 720.

[0052] (iv) Composition of the transport room 800

[0053] like Figure 5As shown, a transfer chamber 800 is configured between the film deposition apparatus 500 and the first cleaning apparatus 600, between the film deposition apparatus 500 and the second cleaning apparatus 700, and between the first cleaning apparatus 600 and the second cleaning apparatus 700, with gate valves 10a to 10c as a barrier. A transfer mechanism 850 for transferring wafers 200 is provided within the transfer chamber 800. The transfer mechanism 850 places the wafers 200 on a substrate mounting section provided on a robotic arm, and transfers the wafers 200 between the film deposition apparatus 500 and the first cleaning apparatus 600, or between the film deposition apparatus 500 and the second cleaning apparatus 700.

[0054] (v) Control Unit

[0055] like Figure 6 As shown, the controller 121, which serves as the control unit (control mechanism) for the film forming apparatus 500, the first cleaning apparatus 600, the second cleaning apparatus 700, and the transfer chamber 800, 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. Furthermore, an external storage device 123 can be connected to the controller 121. It should be noted that the substrate processing apparatus 100 may be configured to have one control unit or multiple control units. That is, a single control unit can be used to control the processing sequence described later, or multiple control units can be used to control the processing sequence described later. Furthermore, multiple control units can be configured as a control system interconnected via a wired or wireless communication network, or the entire control system can be used to control the processing sequence described later. When the term "control unit" is used in this specification, in addition to the case of a single control unit, there are also cases of multiple control units and cases of a control system composed of multiple control units.

[0056] The storage device 121c is configured of, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), or the like. In the storage device 121c, a control program that controls the operation of the substrate processing apparatus 100, a process recipe in which steps, conditions, and the like of the substrate processing described later are described, and the like are recorded and held in a readable manner. The process recipe is a program that functions by causing the substrate processing apparatus 100 to execute each step in the substrate processing described later by the controller 121 and is combined in a manner that a prescribed result can be obtained. Hereinafter, the process recipe, the control program, and the like are collectively referred to as a program (program product). In addition, the process recipe is also referred to as a recipe. In the present specification, the term "program" is used in a case where only the recipe is included, only the control program is included, or both are included. The RAM 121b is configured as a storage area that temporarily holds a program, data, and the like read by the CPU 121a.

[0057] The I / O port 121d is connected to the MFCs 241a to 241e, the valves 243a to 243e, the pressure sensor 245, the APC valve 244, the vacuum pump 246, the gate valves 10a to 10c, the temperature sensors 263, 620, 720, the heaters 207, 630, 730, the conveyance mechanism 850, and the like described above.

[0058] The CPU 121a is configured to be able to read and execute the control program from the storage device 121c and to read the recipe from the storage device 121c in accordance with the input of an operation command from the input output device 122 or the like. The CPU 121a is configured to be able to control the flow rate adjustment operation of each of the various substances (various gases) based on the MFCs 241a to 241e, the opening and closing operation of the valves 243a to 243e, the opening and closing operation of the APC valve 244, the pressure adjustment operation using the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heaters 207, 630, 730 based on the temperature sensors 263, 620, 720, the rotation and rotation speed adjustment operation of the wafer boat 217 based on the rotation mechanism 267, the raising and lowering operation of the wafer boat 217 based on the wafer boat elevator 115, the opening and closing operation of the gate 219s based on the gate opening and closing mechanism 115s, the operation of the conveyance mechanism 850, and the like in accordance with the contents of the recipe read.

[0059] The controller 121 can be configured by installing the above-described program recorded and saved in the external storage device 123 into a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a USB memory, a semiconductor memory such as an SSD, and the like. The storage device 121c and the external storage device 123 are configured as a recording medium that is readable by a computer. Hereinafter, they will be collectively referred to as a recording medium. In the present specification, the term "recording medium" is used in a case where only the storage device 121c is included alone, only the external storage device 123 is included alone, or both are included. Note that the external storage device 123 can not be used, and the provision of the program to the computer can be performed using a communication unit such as the Internet, a dedicated line, or the like.

[0060] (2) Substrate processing step

[0061] A method for processing a substrate using the above-described substrate processing apparatus 100 as one step of a manufacturing process of a semiconductor device, that is, a processing sequence example for forming a film in the first region among the first region and the second region possessed by the wafer 200 will be described. More specifically, a processing sequence example for forming a film in the first region and the third region among the first region, the second region, and the third region possessed by the wafer 200 will be described.

[0062] In the present mode, an example in which the wafer 200 in which a recess such as a trench, a groove, a hole, or the like as a three-dimensional structure is formed on the surface thereof is described. In the present mode, a region of an outer surface (outer surface) constituting the recess and adjacent to an opening of the recess is referred to as a first region. A region of an inner surface constituting the recess and including a bottom surface of the recess is referred to as a second region. A region of the region of the inner surface constituting the recess, which is located on the opening side than the second region and is adjacent to the opening and the second region, is referred to as a third region (see FIG. 1). Figure 7

[0063] ​In the present embodiment, the steps A, B, C described later are sequentially performed. In step A, a wafer 200 having a first region capped with a first end and a second region capped with a first end is prepared (preparation process). Specifically, in step A, a wafer 200 having a first region, a second region, and a third region each capped with a first end is prepared. In step B, the first end in the first region is selectively removed compared with the first end in the second region by supplying a first processing liquid containing a liquid that reacts with the first end to the wafer 200 (removal process). Specifically, in step B, the first end in the first region and the third region is selectively removed compared with the first end in the second region. In step C, a film is selectively formed in the first region compared with the second region by supplying a film forming agent to the wafer 200 (film forming process). Specifically, in step C, a film is selectively formed in the first region and the third region compared with the second region. Each of steps A, B, and C is performed in the film forming apparatus 500. In the following description, the operation of each part of the substrate processing apparatus 100 is controlled by the controller 121.

[0064] In the present specification, the meaning of "selectively removing", "selectively processing" is not limited to the case where only one is removed, processed and the other is not removed, processed at all. The meaning includes the case where the amount, speed, probability, etc. of removal, processing of one is relatively larger than that of the other. In other words, the meaning includes the case where one is preferentially removed, processed compared with the other. Also, the meaning of "selectively forming", "selectively adsorbing" is similarly not limited to the case where only one is formed, adsorbed and the other is not formed, adsorbed at all. The meaning includes the case where the amount, speed, probability, etc. of formation, adsorption of one is relatively larger than that of the other. In other words, the meaning includes the case where one is preferentially formed, adsorbed compared with the other.

[0065] Step A in the present embodiment is the step of:

[0066] (a) preparing a wafer 200 having a first region capped with a first end and a second region capped with a first end, the first region constituting a surface outside a recess and adjacent to an opening of the recess, the second region constituting an inner surface of the recess (see (b) in Figure 7 ).

[0067] Note that, in the present embodiment, the case where, in step A, the following is performed is described.

[0068] (a-0) performing step aO of forming the fourth terminal in the first region and the second region (see (a) in Figure 7

[0069] (a-1) performing step al of forming the first terminal in the first region and the second region by supplying the first modifier to the wafer 200 (see (b) in Figure 7

[0070] Further, in the present mode, the case where, in step aO, the raw material containing

[0071] (a-0a) step aOa of supplying the raw material to the wafer 200, and

[0072] (a-0b) step aOb of supplying the oxidizing agent as the reactant to the wafer 200

[0073] the cycle of steps aOa and aOb is performed a predetermined number of times (n1 times, n1 being an integer of 1 or more), thereby forming an intermediate layer having a surface on which the fourth terminal is formed in the first region and the second region (see (a) in Figure 7

[0074] Step B in the present mode is the following step:

[0075] (b) removing the first terminal of the first region in such a manner that the density of the first terminal in the first region becomes smaller than the density of the first terminal in the second region by supplying the first processing liquid containing a liquid that reacts with the first terminal to the wafer 200 (see (c) in Figure 7

[0076] Step C in the present mode is the following step:

[0077] (c) forming a film in the first region in such a manner that the film formation rate to the first region becomes larger than the film formation rate to the second region by supplying the film formation agent to the wafer 200 after step B (see (d) in Figure 2

[0078] Further, in the present mode, the case where, in step C, the raw material containing

[0079] step cl of supplying the raw material to the wafer 200, and

[0080] step c2 of supplying the oxidizing agent to the wafer 200

[0081] the cycle of steps cl and c2 is performed a predetermined number of times (n2 times, n2 being an integer of 1 or more), thereby forming a film in the first region.

[0082] ​​​​​In the present specification, the above processing sequence is sometimes expressed as follows for the sake of convenience. The same expression is used in the description of the following modification examples, other modes, and the like.

[0083] (raw material → oxidizing agent) x n1→ 1st modifier→ 1st treatment liquid→ (raw material → oxidizing agent) x n2

[0084] The term "wafer" used in the present specification includes a case where the wafer itself is referred to and a case where a laminate of the wafer and a prescribed layer or film formed on the surface of the wafer is referred to. The term "surface of the wafer" used in the present specification includes a case where the surface of the wafer itself is referred to and a case where the surface of a prescribed layer or the like formed on the wafer is referred to. In the present specification, a case where it is described that a prescribed layer is formed on the wafer includes a case where the prescribed layer is directly formed on the surface of the wafer itself and a case where the prescribed layer is formed on a layer or the like formed on the wafer. The case where the term "substrate" is used in the present specification is synonymous with the case where the term "wafer" is used.

[0085] The term "agent" used in the present specification includes at least either one of a gaseous substance and a liquid substance. The liquid substance includes a mist-like substance. That is, each of the film forming agent (raw material, oxidizing agent), the 1st modifier, and the 2nd modifier can include a gaseous substance, can include a liquid substance such as a mist-like substance, or can include both of them.

[0086] The term "layer" used in the present specification includes at least either one of a continuous layer and a discontinuous layer. For example, the 1st to 7th layers, the intermediate layer can include a continuous layer, can include a discontinuous layer, or can include both of them.

[0087] In the present specification, in the case where it is described that the film forming agent (raw material, oxidizing agent), the 1st modifier, and the 2nd modifier respectively perform adsorption to the surface of the wafer 200 and perform reaction, not only a mode in which they perform adsorption and reaction to the wafer surface in an undecomposed state is included, but also a mode in which an intermediate generated by decomposition of them and detachment of a ligand is adsorbed to and reacts with the surface of the wafer 200 is included.

[0088] (Wafer filling and boat loading)

[0089] If a plurality of wafers 200 are filled (wafer filling) in the boat 217 by the conveyance mechanism 850, as shown in FIG. 2B, the boat 217 on which the plurality of wafers 200 are supported is carried into (boat loading) the processing chamber 201 by the boat elevator 115. Figure 7

[0090] (Pressure adjustment and temperature adjustment)

[0091] ​After the end of the boat loading, the vacuum pump 246 is operated to perform vacuum exhaust (depressurization exhaust) so that the inside of the processing chamber 201, i.e., the space in which the wafer 200 is present, becomes a desired pressure (degree of vacuum). At this time, feedback control is performed on the APC valve 244 based on pressure information measured by the pressure sensor 245. In addition, the heater 207 is used to heat the wafer 200 in the processing chamber 201 so that it becomes a desired processing temperature. At this time, feedback control is performed on the energization state of the heater 207 based on temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 becomes a desired temperature distribution. In addition, rotation of the wafer 200 based on the rotation mechanism 267 is started. In addition, the heaters 630, 730 are controlled based on temperature information detected by the temperature sensors 620, 720 so that the first processing liquid, the second processing liquid in the processing tanks 610, 710 become desired temperatures. The exhaust of the inside of the processing chamber 201, the heating and rotation of the wafer 200, and the temperature adjustment of the first processing liquid, the second processing liquid are all performed at least during the period until the end of the processing of the wafer 200.

[0092] Then, the following steps A, B, C are sequentially performed. Note that in step A, the following steps a0, al are sequentially performed.

[0093] [Step A: Preparation Process]

[0094] (Step a0)

[0095] In this step, the wafer 200 is supplied with a raw material and an oxidizing agent. Thereby, an oxide layer (intermediate layer) is formed in the first region and the second region. In this step, specifically, the following steps a0a, a0b are sequentially performed.

[0096] [Step a0a]

[0097] In this step, the wafer 200 in the processing chamber 201 is supplied with a raw material. The raw material used in this step is sometimes referred to as a first raw material, and the raw material supply system that supplies the wafer 200 with the first raw material is sometimes referred to as a first raw material supply system (first raw material exposure system).

[0098] Specifically, the valve 243a is opened, and a raw material is caused to flow into the gas supply pipe 232a. The raw material is flow-regulated by the MFC 241a, supplied into the processing chamber 201 via the nozzle 249a, and exhausted from the exhaust port 231a. At this time, the wafer 200 is supplied with the raw material (raw material supply). At this time, the valves 243d, 243e can also be opened, and a non-reactive gas can be supplied into the processing chamber 201 via the nozzles 249a, 249b, respectively.

[0099] As the processing conditions when the raw material is supplied by this step, the following can be exemplified:

[0100] Treatment temperature: room temperature to 600°C, preferably 50 to 400°C

[0101] Treatment pressure: 1 to 101325 Pa, preferably 1 to 1300 Pa

[0102] Raw material supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm

[0103] Raw material supply time: 1 second to 240 minutes, preferably 30 seconds to 120 minutes

[0104] Non-active gas supply flow rate (per gas supply pipe): 0 to 20 slm.

[0105] Note that the expression of a numerical range such as "50 to 400°C" in this specification means that the lower limit value and the upper limit value are included in the range. Therefore, for example, "50 to 400°C" means "50°C or higher and 400°C or lower". The same applies to other numerical ranges. In addition, the treatment temperature in this specification refers to the temperature of the wafer 200 or the temperature in the processing chamber 201, and the treatment pressure refers to the pressure in the processing chamber 201, in other words, the pressure of the space in which the wafer 200 exists. In addition, the treatment time refers to the time during which the treatment is continued. In addition, in the case where the supply flow rate includes 0 slm, 0 slm means the case where the substance is not supplied. The same applies to the following description.

[0106] By supplying the raw material to the wafer 200 under the above-described treatment conditions, it is possible to cause at least a part of the molecular structure of the molecules constituting the raw material to be adsorbed to the first region and the second region, in detail, to the first region, the second region, and the third region, and to form the first layer in these regions.

[0107] As the raw material, for example, a Si-containing substance containing silicon (Si) as a main element constituting the intermediate layer formed in step a0 can be used. As the Si-containing substance, for example, a substance containing a halogen and Si, that is, a halosilane can be used. The halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), and the like. As the halosilane, for example, chlorosilane, fluorosilane, bromosilane, iodosilane, and the like can be used.

[0108] As the raw material, for example, monochlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), tetrachlorosilane (SiCl4), hexachlorodisilane (Si2Cl6), octachlorotrisilane (Si3Cl8), and the like chlorosilanes can be used.

[0109] As the raw material, besides the above, for example, a substance containing an amino group and Si, i.e., an amino silane can be used. The amino group refers to a monovalent functional group obtained by removing H from ammonia, a primary amine, or a secondary amine, and can be represented as -NH2, -NHR, -NR2. Note that R represents an alkyl group, and the two R's of -NR2may be the same or different.

[0110] As the raw material, for example, 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), (diisopropylamino)silane (SiH3[N(C3H7)2]), and the like amino silane can be used.

[0111] As the raw material, one or more of the above can be used.

[0112] As the non-active gas, a noble gas such as nitrogen (N2), argon (Ar), helium (He), neon (Ne), xenon (Xe), or the like can be used. As the non-active gas, one or more of these can be used. This is also the same in each of the steps described later.

[0113] After the first to third regions in the wafer 200 are formed with the first layer, the valve 243a is closed, and the supply of the raw material into the processing chamber 201 is stopped. In addition, the processing chamber 201 is vacuum-exhausted, and the gaseous substance or the like remaining in the processing chamber 201 is removed from the processing chamber 201. At this time, the valves 243d and 243e are opened, and the non-active gas is supplied into the processing chamber 201 via the nozzles 249a and 249b. The non-active gas functions as a purge gas, and thus the space in which the wafer 200 exists, i.e., the processing chamber 201 is purged.

[0114] [Step a0b]

[0115] After the step a0a is completed, the wafer 200 in the processing chamber 201, i.e., the wafer 200 after the first to third regions are formed with the first layer, is supplied with an oxidizing agent as a reactant. The oxidizing agent used in this step is sometimes referred to as a first reactant or a first oxidizing agent, and the reactant supply system or the oxidizing agent supply system for supplying the first reactant or the first oxidizing agent to the wafer 200 is sometimes referred to as a first reactant supply system or a first oxidizing agent supply system (a first reactant exposure system or a first oxidizing agent exposure system).

[0116] Specifically, the valve 243b is opened, and the oxidizing agent is caused to flow into the gas supply pipe 232b. The oxidizing agent is flow-regulated by the MFC 241b, and is supplied into the processing chamber 201 via the nozzle 249b, and is exhausted from the exhaust port 231a. At this time, the wafer 200 is supplied with the oxidizing agent (oxidizing agent supply).

[0117] As the processing conditions when the oxidizing agent is supplied in this step, for example, the following can be exemplified:

[0118] Oxidizing agent supply flow rate: 0.001 to 20 slm, preferably 0.001 to 10 slm

[0119] Oxidizing agent supply time: 1 second to 240 minutes, preferably 30 seconds to 120 minutes.

[0120] The other processing conditions can be set to be the same as those when the raw material is supplied in step a0a.

[0121] By supplying the oxidizing agent to the wafer 200 under the above processing conditions, at least a part of the first layer formed in the first to third regions can be oxidized. Thereby, the second layer is formed in the first to third regions, which is formed by oxidizing the first layer and forming OH group (hydroxyl group) as a terminal (OH terminal).

[0122] As the oxidizing agent, for example, an O-containing (O) substance can be used. As the O-containing substance, for example, oxygen (O2), ozone (O3), nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), carbon monoxide (CO), carbon dioxide (CO2), or the like can be used. As the oxidizing agent, one or more of these can be used.

[0123] In addition, as the oxidizing agent, for example, an O- and H-containing substance can be used. As the O- and H-containing gas, for example, water vapor (H2O), hydrogen peroxide (H2O2), H2+O2, H2+O3, or the like can be used. That is, as the O- and H-containing substance, an O-containing substance + an H-containing substance can also be used. In this case, instead of the H-containing substance, a deuterium (D)-containing substance can also be used. As the D-containing substance, deuterium (D2) can also be used. As the oxidizing agent, one or more of these can be used.

[0124] In addition, in the present specification, "H2+O2" is collectively described as a mixture of H2and O2. In the case of supplying the mixture, it can be supplied into the processing chamber 201 after mixing the two substances in the supply pipe, or the two substances can be supplied into the processing chamber 201 from different supply pipes and mixed in the processing chamber 201.

[0125] After converting the first layer formed in the first to third regions of the wafer 200 into the second layer, the valve 243b is closed and the supply of the oxidizing agent into the processing chamber 201 is stopped. In addition, by the same processing steps and processing conditions as the purge in step a0a, the gaseous substance or the like remaining in the processing chamber 201 is excluded from the processing chamber 201.

[0126] [Prescribed number of times]

[0127] By sequentially performing the above-mentioned steps a0a, a0b cyclically n1 times (n1 is an integer of 1 or more) non-simultaneously, that is, asynchronously, an intermediate layer can be formed in the first region and the second region, specifically, the first region, the second region, and the third region of the wafer 200. For example, in the case of using the above-mentioned raw material and oxidizing agent, a SiO layer, for example, can be formed as the intermediate layer in the first to third regions. Thus, an intermediate layer having a surface in which OH terminals as the fourth terminals are formed (see (a) in Figure 7 In other words, the fourth terminals can be formed in the first to third regions. The fourth terminals formed in the first to third regions function as adsorption sites of the first modifier to be supplied in the step a1 described later. That is, the intermediate layer having the fourth terminals functions as an adsorption promoting layer for the first modifier. The above-mentioned cycle is preferably repeated a plurality of times until the film thickness of the intermediate layer formed by laminating the second layer becomes a desired film thickness.

[0128] (Step a1)

[0129] After the step a0 is completed, the wafer 200 in the processing chamber 201, that is, the wafer 200 in which the intermediate layer is formed in the first to third regions is supplied with the first modifier.

[0130] Specifically, the valve 243c is opened, and the first modifier is caused to flow into the gas supply pipe 232c. The first modifier is flow-regulated by the MFC 241c, supplied into the processing chamber 201 via the nozzle 249a, and exhausted from the exhaust port 231a. At this time, the wafer 200 is supplied with the first modifier. At this time, the valves 243d and 243e can also be opened, and the non-active gas can be supplied into the processing chamber 201 via the nozzles 249a and 249b, respectively.

[0131] As the processing conditions when the first modifier is supplied in the present step, the following can be exemplified:

[0132] Processing temperature: 25 to 500°C, preferably 50 to 300°C

[0133] Processing pressure: 1 to 13300 Pa, preferably 50 to 1330 Pa

[0134] First modifier supply flow rate: 0.01 to 3 slm, preferably 0.5 to 1 slm

[0135] First modifier supply time: 0.1 seconds to 120 minutes, preferably 30 seconds to 60 minutes.

[0136] The other processing conditions can be set to be the same as those when the raw material is supplied in the step a0a.

[0137] By supplying the first modifier to the wafer 200 under the above processing conditions, at least a part of the molecular structure of the molecule constituting the first modifier can be adsorbed to the first region and the second region, specifically the first to third regions, of the wafer 200, forming a third layer (an adsorption inhibition layer). Specifically, the fourth terminal (OH terminal) formed in the first to third regions can be allowed to react with the first modifier, and at least a part of the molecular structure of the molecule constituting the first modifier can be adsorbed to the first to third regions. Thereby, the first to third regions can be capped with at least a part of the molecular structure of the molecule constituting the first modifier. As at least a part of the molecular structure of the molecule constituting the first modifier, for example, a residue (e.g., Si-H) including a bond of an atom (e.g., Si) that reacts with the fourth terminal and a hydrogen group (H group), or a residue (e.g., Si-OR) in which an atom that reacts with the fourth terminal is bonded to an alkoxy group can be exemplified. In the case of being capped with these residues, an H terminal, an alkoxy terminal (see (b) in FIG. 1) as the first terminal is formed in the first to third regions. The first terminal formed in the first to third regions is a terminal that imparts hydrophobicity to the top surface of the wafer 200, and in the step C to be described later, functions as an inhibitor that hinders adsorption of the film former to the surface of the wafer 200. Figure 7

[0138] As the first modifier, for example, a substance in which hydrogen (H) and an amino group are bonded to Si, i.e., an amino silane such as 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]), (diisoamylamino)silane (SiH3[N(C5H 11 Particularly preferably, a substance in which three H and one amino group are bonded to Si, i.e., a monoamino silane such as (diisobutylamino)silane, (diisopropylamino)silane, or the like is used. By using a monoamino silane as the first modifier, thereby, in this step, the H terminal can be formed more uniformly and sufficiently on the first surface.

[0139] ​Further, as the first modifier, for example, (dimethylamino)trimethoxysilane (Si(OCH3)3[N(CH3)2]), (dimethylamino)triethoxysilane (Si(OC2H5)3[N(CH3)2]), (dimethylamino)tripropoxysilane (Si(OC3H7)3[N(CH3)2]), (dimethylamino)tributoxysilane (Si(OC4H9)3[N(CH3)2]), or the like, in which an alkoxyl group and an amino group are bonded to Si, can be used. In particular, it is preferable to use a substance in which three alkoxyl groups and one amino group are bonded to Si. By using such a substance as the first modifier, the alkoxyl group terminal can be formed more uniformly and sufficiently on the first surface in this step.

[0140] As the first modifier, one or more of the above can be used.

[0141] After the first terminal is formed on the first to third regions of the wafer 200, the valve 243c is closed, and the supply of the first modifier into the processing chamber 201 is stopped. Further, by the same processing steps and processing conditions as the purge in step a0a, the gaseous substance or the like remaining in the processing chamber 201 is removed from the processing chamber 201.

[0142] (Post-purge and atmospheric pressure recovery)

[0143] After step a1 is completed, a non-reactive gas as a purge gas is supplied from each of the nozzles 249a, 249b into the processing chamber 201, and is exhausted from the exhaust port 231a. Thereby, the processing chamber 201 is purged, and the gaseous substance or the like remaining in the processing chamber 201 is removed from the processing chamber 201 (post-purge). Then, the atmosphere in the processing chamber 201 is replaced with the non-reactive gas, and the pressure in the processing chamber 201 is recovered to the normal pressure (atmospheric pressure recovery).

[0144] (Wafer boat unloading and wafer extraction)

[0145] After that, the seal cap 219 is lowered by the wafer boat lifter 115, and the lower end of the manifold 209 opens the opening. Further, the wafer 200 is carried out to the outside of the reaction tube 203 in a state of being supported by the wafer boat 217 from the lower end of the manifold 209 (wafer boat unloading). After the wafer 200 is carried out to the outside of the reaction tube 203, it is extracted from the wafer boat 217 by the carrying mechanism 850 (wafer extraction).

[0146] The wafer 200 extracted from the wafer boat 217 is placed on a not-shown placement table provided in the first cleaning device 600 via the carrying chamber 800 by the carrying mechanism 850.

[0147] [Step B: removal process]

[0148] In this step, the wafer 200 in the first cleaning device 600, i.e., the wafer 200 in which the first end is formed in the first to third regions, is supplied with the first treatment liquid containing a liquid that reacts with the first end.

[0149] Specifically, the wafer 200 is exposed to the first treatment liquid supplied via the treatment liquid supply pipe 640 and stored in the treatment tank 610. More specifically, the wafer 200 placed on the placement table in the first cleaning device 600 is immersed in the first treatment liquid stored in the treatment tank 610 by a non-illustrated moving mechanism provided in the first cleaning device 600.

[0150] As the treatment conditions when the first treatment liquid is supplied (i.e., exposed to the first treatment liquid) in this step, the following can be exemplified:

[0151] Exposure temperature: 0 to 100°C, preferably 15 to 50°C

[0152] Exposure time: 0.1 seconds to 120 minutes, preferably 30 seconds to 60 minutes.

[0153] Note that the exposure temperature in the present specification refers to the temperature of the wafer 200 in the treatment liquid or the temperature of the treatment liquid. The exposure time refers to the time for which exposure is continued, specifically, the supply time of the treatment liquid. The same applies to the following description.

[0154] By supplying the first treatment liquid to the wafer 200 under the above treatment conditions, the first end of the first region can be removed (destroyed, modified) in such a manner that the density of the first end in the first region becomes smaller than the density of the first end in the second region. In addition, the first end of the third region can be removed in such a manner that the density of the first end in the third region becomes smaller than the density of the first end in the second region. In other words, the first end formed in the first and third regions can be selectively removed compared to the first end formed in the second region. Specifically, the first end formed in the second region can be left and the first end formed in the first and third regions can be removed. For example, in the case where a liquid containing a compound having an OH end in the molecule is used as the liquid that reacts with the first end, the first end (H end) in the first and third regions can be replaced with the OH end as the second end (see (c) in Figure 6 In this case, the first end that hinders the adsorption of the film forming agent to be supplied in the step C described later can be left in the second region, and the second end that functions as an adsorption site of the film forming agent to be supplied in the step C can be formed in the first and third regions.

[0155] The first processing liquid is either a liquid that reacts with the first terminal or a liquid containing the liquid that reacts with the first terminal and an additive that causes a change (increase or decrease) in the surface tension of that liquid. In this embodiment, an example using an additive that reduces the surface tension of the liquid will be described. The additive that reduces the surface tension of the liquid that reacts with the first terminal has a surface tension lower than that of the liquid that reacts with the first terminal, or it has the effect of reducing the surface tension of the liquid that reacts with the first terminal by mixing with it. The first processing liquid, by containing the liquid that reacts with the first terminal and the additive, becomes a liquid with a surface tension lower than that of the liquid that reacts with the first terminal.

[0156] As the liquid that reacts with the first terminal, liquids containing compounds with OH terminals, such as H2O and H2O2, can be used. Especially when the first terminal contains an H terminal, by using liquids of these compounds as the liquid that reacts with the first terminal, the H terminal can be effectively removed. One or more of these compounds can be used as the liquid that reacts with the first terminal. Furthermore, by using a liquid containing a compound with an OH terminal as the liquid that reacts with the first terminal, the reacted H terminal (first terminal) can be replaced with an OH terminal (second terminal).

[0157] Furthermore, as the liquid that reacts with the first terminal, a liquid containing H2O can be used as the first treatment liquid, and a liquid further containing H2O2 (i.e., also known as an aqueous hydrogen peroxide solution) can be used. By using a liquid that also contains H2O2 as the first treatment liquid, the effect of removing the first terminal formed in the first and third regions can be further improved.

[0158] As additives, compounds containing the structural formula R-COH, such as alkyl ethers like polyoxyethylene alkyl ethers, polyol ethers like alkyl glycosides, and fatty acid esters like sorbitan fatty acid esters, can be used. It should be noted that R here can also be at least one of carbon (C), hydrogen (H), oxygen (O), nitrogen (N), and fluorine (F), or at least one of C, H, and O.

[0159] Additionally, as an additive, for example, a mixture containing C can be used. m H (2m+2) The alkanes shown (especially alkane series hydrocarbons) or C m H 2m An additive of at least one of the following: a compound formed by replacing one or more H atoms of an olefin (especially a chain olefin hydrocarbon) with OH (i.e., also called an alcohol), and a compound formed by replacing one or more H atoms of an aromatic hydrocarbon with OH (i.e., also called a phenol).

[0160] Further, as the additive, for example, an additive containing one or more compounds selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol can be used. Note that H2O contained in ethanol as an impurity sometimes functions as the liquid that reacts with the first end in the first treatment liquid.

[0161] Further, as the additive, in addition to the above, for example, an optional surfactant that can reduce the surface tension of the liquid that reacts with the first end can be used.

[0162] For at least any one of the surface tension of the first treatment liquid, the supply time of the first treatment liquid, and the temperature of the first treatment liquid, adjustment corresponding to at least any one of (i) the distance d1 from the opening of the recess at the position farthest from the opening in the third region (see Figure 6 ), (ii) the width w of the opening (see Figure 7 ), and (iii) the kind of the first end is preferable. For example, the longer the distance d1, the smaller the width w of the opening, or the greater the hydrophobicity of the first end, the more difficult the penetration of the first treatment liquid into the inside of the recess. Therefore, in this case, at least any one of a) reducing the surface tension of the first treatment liquid (for example, increasing the concentration of the additive), b) extending the supply time of the first treatment liquid, c) increasing the temperature of the first treatment liquid is preferably performed. In contrast, for example, the shorter the distance d1, the greater the width w of the opening, or the smaller the hydrophobicity of the first end, the easier the penetration of the first treatment liquid into the inside of the recess. Therefore, in this case, at least any one of a') increasing the surface tension of the first treatment liquid (specifically, reducing the concentration of the additive in the first treatment liquid), b') shortening the supply time of the first treatment liquid, c') reducing the temperature of the first treatment liquid is preferably performed. Thus, at least any one of the surface tension, the supply time, and the temperature of the first treatment liquid is preferably adjusted so that the first treatment liquid can penetrate the third region.

[0163] For example, when water is used as the liquid that reacts with the first end and ethanol is used as the additive, the concentration of the additive in the first treatment liquid is, for example, 0 to 99.9%, and is preferably 0 to 90%. A concentration of 0% means a case where the first treatment liquid does not contain the additive. Further, as to the concentration of the additive, a concentration that makes the contact angle of the first treatment liquid to the first to third regions whose surfaces are capped with the first end 10 to 100°, and preferably 10 to 90° can be exemplified.

[0164] After the first end in the first region and the third region of the wafer 200 is selectively removed and replaced with the second end, the wafer 200 is lifted from the processing tank 610 by the moving mechanism, and is placed on a placement table in the first cleaning device 600. The wafer 200 placed on the placement table is carried out to the outside of the first cleaning device 600 by the carrying mechanism 850, and is loaded in the wafer boat 217 via the carrying chamber 800.

[0165] (Wafer filling and wafer boat loading)

[0166] After that, the wafer 200 is loaded in the wafer boat 217 and carried into the processing chamber 201 by the same steps as the wafer filling and wafer boat loading described above.

[0167] (Pressure adjustment and temperature adjustment)

[0168] Then, the pressure and the temperature in the processing chamber 201 are adjusted by the same steps as the pressure adjustment and the temperature adjustment described above.

[0169] [Step C: Film forming process]

[0170] In this step, the wafer 200 is supplied with a raw material and an oxidizing agent as film forming agents. Thereby, a film is selectively formed in the first region and the third region. In this step, specifically, the following step cl and step c2 are sequentially performed.

[0171] [Step cl]

[0172] After the end of the step B, the wafer 200 carried into the processing chamber 201 in the film forming device 500 from the first cleaning device 600, that is, the wafer 200 after the second end is selectively formed in the first region and the third region, is supplied with a raw material. In this step, the wafer 200 can be supplied with a raw material by the same processing steps and processing conditions as the raw material supply in the step a0a. The raw material used in this step is sometimes referred to as a second raw material.

[0173] By supplying the wafer 200 with a raw material under the processing conditions described above, at least a part of the molecular structure of the molecules constituting the raw material can be selectively adsorbed to the first region and the third region in which the second end is formed, and a fourth layer can be selectively formed in these regions. At this time, the adsorption of at least a part of the molecular structure of the molecules constituting the raw material to the second region is inhibited by the adsorption inhibition effect of the first end formed in the second region.

[0174] Further, as the raw material (2nd raw material) to be supplied to the wafer 200 in this step, one or more of the gases exemplified in the example of the raw material (1st raw material) to be supplied to the wafer 200 in the step aOa can be used. The 2nd raw material can be the same as the 1st raw material, or can be different. When a raw material different from the 1st raw material is used as the 2nd raw material, a 2nd raw material supply system (2nd raw material exposure system) configured to supply the 2nd raw material is further provided. Like the raw material supply system described above, the 2nd raw material supply system is configured, for example, by a gas supply pipe connected to a nozzle 249a, an MFC, and a valve.

[0175] After the 4th layer is selectively formed in the 1st region and the 3rd region of the wafer 200, the valve 243a is closed, and the supply of the raw material into the processing chamber 201 is stopped. Then, by the same processing steps and processing conditions as the purge in the step aOa, the gas-like substance and the like remaining in the processing chamber 201 are removed from the processing chamber 201.

[0176] [Step c2]

[0177] After the end of the step cl, an oxidizing agent as a reactant is supplied to the wafer 200 in the processing chamber 201, that is, the wafer 200 after the 4th layer is selectively formed in the 1st region and the 3rd region. In this step, the oxidizing agent can be supplied to the wafer 200 by the same processing steps and processing conditions as the supply of the oxidizing agent in the step aOb. The oxidizing agent used in this step is sometimes referred to as a 2nd reactant or a 2nd oxidizing agent.

[0178] By supplying the oxidizing agent to the wafer 200 under the above processing conditions, at least a part of the 4th layer formed in the 1st region and the 3rd region in the step cl can be oxidized. Thus, a 5th layer is formed in the 1st region and the 3rd region, the 5th layer being formed by oxidizing the 4th layer and forming OH terminals on the surface.

[0179] Further, as the oxidizing agent (2nd oxidizing agent) to be supplied to the wafer 200 in this step, one or more of the gases exemplified in the example of the oxidizing agent (1st oxidizing agent) to be supplied to the wafer 200 in the step aOb can be used. The 2nd oxidizing agent can be the same as the 1st oxidizing agent, or can be different. When an oxidizing agent different from the 1st oxidizing agent is used as the 2nd oxidizing agent, a 2nd oxidizing agent supply system (2nd oxidizing agent exposure system) configured to supply the 2nd oxidizing agent is further provided. Like the oxidizing agent supply system described above, the 2nd oxidizing agent supply system is configured, for example, by a gas supply pipe connected to a nozzle 249b, an MFC, and a valve.

[0180] After the fourth layer formed in the first region and the third region of the wafer 200 is converted into the fifth layer, the valve 243b is closed, and the supply of the oxidizing agent into the processing chamber 201 is stopped. Then, the gaseous substance and the like remaining in the processing chamber 201 are removed from the processing chamber 201 by the same processing steps and processing conditions as those in the purge in step a0a.

[0181] [Regulation number of times]

[0182] By sequentially performing the above-described steps cl, c2, which are not performed simultaneously, n2 times (n2 is an integer of 1 or more), a film can be formed in the first region in such a manner that the film formation rate in the first region becomes greater than the film formation rate in the second region. In addition, a film can be formed in the third region in such a manner that the film formation rate in the third region becomes greater than the film formation rate in the second region. In other words, a film can be selectively formed in the first region and the third region of the wafer 200 (see (d) in Figure 6 In detail, while the film formation in the second region, which is the region on the inside (deep portion) side of the recess, is suppressed, a film can be selectively formed in the first region and the third region, which are the regions on the opening side of the recess. The above-described cycle is preferably repeated a plurality of times until the film thickness of the film formed by laminating the fifth layer becomes a desired film thickness. In addition, it is preferable that the film formed in the first region and the third region occlude the opening of the recess by repeating the above-described cycle a plurality of times, whereby an air gap is formed in the recess.

[0183] After the completion of step C, post purge, atmospheric pressure recovery, boat unloading, and wafer extraction are sequentially performed. The details are the same as those of the steps performed after step A.

[0184] (3) Effects of the present mode

[0185] According to the present mode, one or more of the effects shown below can be obtained.

[0186] (a) In step B, by removing the first end of the first region in such a manner that the density of the first end in the first region becomes less than the density of the first end in the second region, free film formation can be achieved in these regions. For example, in step C performed after steps A and B, a film can be selectively formed in the first region compared to the second region.

[0187] (b) In step B, by removing the first end of the third region in such a manner that the density of the first end in the third region becomes less than the density of the first end in the second region, free film formation can be achieved in these regions. For example, in step C performed after steps A and B, a film can be selectively formed in the third region compared to the second region.

[0188] (c) By including an additive that changes (e.g., reduces) the surface tension of the liquid that reacts with the first end in the first treatment liquid, the first treatment liquid is able to easily penetrate into the inside of the recess. Furthermore, by adjusting the amount of the additive in the first treatment liquid, etc., the first treatment liquid is able to easily penetrate into a desired region (deep region, shallow region) inside the recess. Thus, more free film formation in the first region to the third region is able to be achieved.

[0189] (d) In step B, at least one of (i) the distance d1 from the opening (see Figure 6 ) at the position farthest from the opening in the third region, (ii) the width w of the opening (see Figure 8 ), and (iii) the kind of the first end, is adjusted to at least one of the surface tension of the first treatment liquid, the supply time of the first treatment liquid, and the temperature of the first treatment liquid. Thus, while leaving the first end in the predetermined second region, the first end in the predetermined first region and third region is able to be removed with good precision. That is, since the first end in the first region and third region, which are desired regions, is able to be removed with good precision, the precision of the regions (i.e., the first region and third region) in which the film is selectively formed in step C is able to be improved. In other words, by these adjustments, the boundary position of the region in which the first end is removed (i.e., the second region) and the region in which the first end is left (i.e., the third region) is able to be controlled (determined).

[0190] (e) In step C, by supplying a film formation agent to the wafer 200 after step B, a film is formed in the first region in such a manner that the film formation speed in the first region becomes greater than the film formation speed in the second region. Thus, a film is able to be selectively formed in the first region compared to the second region.

[0191] (f) In step C, by supplying a film formation agent to the wafer 200 after step B, a film is formed in the third region in such a manner that the film formation speed in the third region becomes greater than the film formation speed in the second region. Thus, a film is able to be selectively formed in the third region compared to the second region.

[0192] (g) The first end hinders the adsorption of the film formation agent to the top surface of the wafer 200, and thus, in step C, a film is able to be more selectively formed in the first region and third region.

[0193] (h) The first end is an end that imparts hydrophobicity to the top surface of the wafer 200, and thus, in step B, the density of the first end in the first region (in detail, the first region and third region) is able to be reliably made smaller than the density of the first end in the second region. This is explained below.

[0194] In the case where the first end, which is the end that imparts hydrophobicity to the surface of the wafer 200, is formed on the inner / bottom side (the second region) of the recess, the penetration of the first treatment liquid into the second region becomes difficult. This is more pronounced in the case where the first end, which is the hydrophobic end, is formed on the opening side (the first region, the third region) of the recess. Therefore, in step B, the penetration of the first treatment liquid into the second region becomes difficult, and thus the first end in the first region and the third region can be selectively removed. Thus, the density of the first end in the first region and the third region can be reliably made lower than the density of the first end in the second region.

[0195] (4) Modification

[0196] The substrate processing sequence in the present embodiment can be changed as in the following modifications. These modifications can be arbitrarily combined.

[0197] (Modification 1)

[0198] In the above embodiment, an example in which the first end formed in the first region and the third region is removed in step B is described, but the present application is not limited to this. For example, in step B, only the first end formed in the first region can be removed (see (c) in Figure 8 ).

[0199] In the present modification, the same effects as in the above embodiment can be obtained. Further, according to the present modification, in step C, the film formation to the inner surface of the recess is hindered, and the deposited film on the upper surface of the recess is formed in a manner that protrudes toward the opening of the recess (see (d) in Figure 9 , and thus is particularly effective in the case where a large air gap is desired to be formed.

[0200] (Modification 2)

[0201] In the above embodiment, an example in which the first end formed in the first region and the third region is removed in step B is described, but the present application is not limited to this. For example, in step B, only the first end formed in the first region can be removed (see (c) in

[0202] (Modification 3)

[0203] In the above embodiment, an example in which the first end formed in the first region and the third region is removed in step B is described, but the present application is not limited to this. For example, in step B, only the first end formed in the first region can be removed (see (c) in

[0204] The same effects as the above-described mode can be obtained in this modification. Furthermore, in this modification, since film formation processing at a low temperature can be achieved, in the execution of the step C, detachment of the first end in the second region can be suppressed. Thus, in the step C, a film can be formed more selectively in the first region (the first region and the third region).

[0205] <2nd Mode of the Invention>

[0206] Next, a 2nd mode of the invention will be described. Mainly, the differences from the above-described 1st mode will be described, and as to other aspects, the description will be omitted.

[0207] (1) Substrate processing procedure

[0208] In this mode, a method for processing a substrate by using the substrate processing apparatus 100 as one procedure of a manufacturing procedure of a semiconductor device, that is, a processing procedure example for forming a film in the second region among the first region and the second region possessed by the wafer 200 will be described. More specifically, a processing procedure example for forming a film in the second region among the first region, the second region, and the third region possessed by the wafer 200 will be described.

[0209] In the processing procedure of this mode, after the steps A and B described in the above-described mode are sequentially performed:

[0210] (d) a step D (modification procedure) of forming a third end in the first region by supplying a second modifier to the wafer 200 after the step B;

[0211] (e) a step E (removal procedure) of removing the first end of the second region by supplying a second processing liquid containing a liquid that reacts with the first end and having a smaller surface tension than the first processing liquid to the wafer 200 after the step D; and

[0212] (f) a step F (film formation procedure) of forming a film in the second region in such a manner that the film formation speed for the second region becomes greater than the film formation speed for the first region and the third region by supplying a film formation agent to the wafer 200 after the step D.

[0213] In addition, in this mode, a case where, in the step F, a film is formed in the second region by repeating a cycle of

[0214] a step f1 of supplying a raw material to the wafer 200, and

[0215] a step f2 of supplying an oxidizing agent as a reactant to the wafer 200

[0216] for a predetermined number of times (n3 times, n3 is an integer of 1 or more), will be described.

[0217] Separately, steps D, F are performed in the film formation device 500, and step E is performed in the 2nd cleaning device 700.

[0218] For convenience, the above processing sequence can also be expressed as follows.

[0219] (raw material → oxidizer) x nl → 1st modifier → 1st treatment liquid → 2nd modifier → 2nd treatment liquid → (raw material → oxidizer) x n3

[0220] After steps A, B are performed, wafer filling and boat loading, pressure adjustment and temperature adjustment are performed, and thereafter, the following steps D, E, F are sequentially executed. Wafer filling and boat loading, pressure adjustment and temperature adjustment, steps A, B in this mode can be performed similarly to those in the above 1st mode, and thus the description thereof is omitted.

[0221] [Step D: modification step]

[0222] After step B is completed, the wafer 200, which is moved from the 1st cleaning device 600 into the processing chamber 201 in the film formation device 500, i.e., the wafer 200 on which the 2nd end is selectively formed in the 1st and 3rd regions, is supplied with the 2nd modifier.

[0223] Specifically, the valve 243c is opened, and the 2nd modifier is caused to flow into the gas supply pipe 232c. The 2nd modifier is flow-adjusted by the MFC 241c, and is supplied into the processing chamber 201 via the nozzle 249a, and is exhausted from the exhaust port 231a. At this time, the wafer 200 is supplied with the 2nd modifier (2nd modifier supply). At this time, the valves 243d, 243e can also be opened, and the non-active gas can be supplied into the processing chamber 201 via the nozzles 249a, 249b, respectively.

[0224] As the processing conditions at the time of supplying the 2nd modifier in this step, the following can be exemplified:

[0225] Processing temperature: room temperature (25°C) to 500°C, preferably room temperature to 250°C

[0226] Processing pressure: 5 to 2000 Pa, preferably 10 to 1000 Pa

[0227] 2nd modifier supply flow rate: 1 to 3 slm, preferably 1 to 0.5 slm

[0228] 2nd modifier supply time: 1 second to 120 minutes, preferably 30 seconds to 60 minutes Non-active gas supply flow rate (per gas supply pipe): 0 to 20 slm.

[0229] By supplying the second modifier to the wafer 200 under the above processing conditions, it is possible to selectively cause at least a part of the molecular structure of the molecule constituting the second modifier to be adsorbed to the first region (in detail, the first region and the third region), and to selectively form a sixth layer (an adsorption inhibition layer) in the first region and the third region. Specifically, it is possible to cause the second terminal formed in the first region and the third region to react with the second modifier while inhibiting at least a part of the molecular structure of the molecule constituting the second modifier from being adsorbed to the second region, and to cause at least a part of the molecular structure of the molecule constituting the second modifier to be selectively adsorbed to the first region and the third region. Thus, it is possible to cap the first region and the third region with at least a part of the molecular structure of the molecule constituting the second modifier. As at least a part of the molecular structure of the molecule constituting the second modifier, for example, a residue including a bond between an atom (for example, Si) that reacts with the second terminal and an alkyl group (for example, a methyl group (Me group), an ethyl group (Et group), a tertiary butyl group (tertiary Bu group)) can be exemplified. More specifically, as such a residue, for example, trimethylsilyl group (Si-Me3), triethylsilyl group (Si-Et3), tertiary butyldimethylsilyl group (Si-(CH3)2C(CH3)3) can be exemplified. In this case, the Si of these silyl groups included in the second modifier is bonded to the O of the second terminal (OH terminal, OH group) in the first region and the third region, and an alkyl terminal as the third terminal is formed in the first region and the third region (see (d) in FIG. 6). In this case, it is possible to leave the first terminal that inhibits the adsorption of the film forming agent supplied in the step F described later in the second region, while forming the third terminal that inhibits the adsorption of the film forming agent supplied in the step F in the first region and the third region. Figure 9

[0230] The first terminal formed in the second region and the third terminal formed in the first region and the third region are both terminals that impart hydrophobicity (that is, water repellency) to the top surface of the wafer 200 (hydrophobic terminals). In addition, among the first terminal such as the H terminal and the third terminal such as the alkyl terminal, the hydrophobicity of the third terminal is greater than that of the first terminal, and thus the hydrophobicity of the first region and the third region in which the third terminal is formed becomes greater (that is, the hydrophilicity becomes smaller) than that of the second region in which the first terminal is formed.

[0231] In addition, the first terminal is removed from the second region by reacting with the second processing liquid supplied to the wafer 200 in the step E described later. On the other hand, compared to the first terminal, the third terminal is less likely to react with the second processing liquid and is less likely to be removed from the first region and the third region. That is, compared to the third terminal, the first terminal is more likely to react with the second processing liquid and is more likely to be selectively removed.

[0232] ​As the 2nd modifying agent, a substance in which an amino group and an alkyl group are bonded to Si, i.e., an alkylaminosilane, 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), (diisopropylamino)trimethylsilane ((C3H7)2NSi(CH3)3), and the like, can be used. In particular, a substance in which 3 alkyl groups and 1 amino group are bonded to Si, i.e., a trialkylaminosilane, such as (dimethylamino)trimethylsilane, (diethylamino)triethylsilane, and the like, is preferably used. One or more of these can be used as the 2nd modifying agent.

[0233] After the 3rd end is selectively formed in the 1st region and the 3rd region of the wafer 200, the valve 243c is closed, and the supply of the 2nd modifying agent into the processing chamber 201 is stopped. Then, the gas-like substance and the like remaining in the processing chamber 201 are removed from the processing chamber 201 by the same processing steps and processing conditions as the purge in step a0a of the above-described 1st method.

[0234] After step D is completed, post-purge, atmospheric pressure recovery, wafer boat unloading, and wafer extraction are sequentially performed. The details are the same as the operations performed after step A.

[0235] The wafer 200 extracted from the wafer boat 217 by the transfer mechanism 850 is placed on an unillustrated placement table provided in the 2nd cleaning device 700 via the transfer chamber 800.

[0236] [Step E: Removal Process]

[0237] In this step, the wafer 200 in the 2nd cleaning device 700, i.e., the wafer 200 in which the 3rd end is formed in the 1st region and the 3rd region and the 1st end is formed in the 2nd region, is supplied with a 2nd processing liquid containing a liquid that reacts with the 1st end and has a surface tension smaller than that of the 1st processing liquid.

[0238] Specifically, the wafer 200 is exposed to the 2nd processing liquid supplied via the processing liquid supply pipe 740 and stored in the processing tank 710. More specifically, the wafer 200 placed on the placement table in the 2nd cleaning device 700 is immersed in the 2nd processing liquid stored in the processing tank 710 by an unillustrated moving mechanism provided in the 2nd cleaning device 700.

[0239] As the processing conditions when the 2nd processing liquid is supplied (i.e., exposure to the 2nd processing liquid) in this step, the following can be exemplified:

[0240] Exposure temperature: 0 to 100°C, preferably 15 to 50°C

[0241] Exposure time: 1 second to 120 minutes, preferably 30 seconds to 60 minutes.

[0242] By supplying the second treatment liquid to the wafer 200 under the above treatment conditions, the first end in the second region can be removed (made to be destroyed, modified) in a manner that the density of the first end in the second region becomes smaller than the density of the third end in the first region (in detail, the first region and the third region). In other words, the first end formed in the second region can be selectively removed compared to the third end formed in the first region and the third region. Specifically, the third end formed in the first region and the third region can be left, and the first end formed in the second region can be removed. For example, when a liquid in which a compound containing an OH end in a molecule is used as the liquid that reacts with the first end, the first end (H end) in the second region can be replaced with the OH end as the fifth end (see (e) in Figure 6 In this case, while the third end that hinders adsorption of a film forming agent to be supplied in a step F described later can be left in the first region and the third region, the fifth end (OH end) that functions as an adsorption site of the film forming agent to be supplied in the step F can be formed in the second region.

[0243] The second treatment liquid is a liquid that contains a liquid that reacts with the first end and an additive that changes the surface tension of the liquid. In the present mode, an example in which an additive that lowers the surface tension of the liquid is used will be described. The additive that lowers the surface tension of the liquid that reacts with the first end and the liquid that reacts with the first end can be the same as or different from those described in the first mode.

[0244] It is preferable that the distance d2 (see Figure 6 ) from the opening to the bottom of the recess, (ii) the width w (see Figure 9at least one of the surface tension of the second treatment liquid, the supply time of the second treatment liquid, and the temperature of the second treatment liquid. For example, the longer the distance d2, the smaller the width w of the opening, or the greater the hydrophobicity of the first end, the third end, the more difficult the second treatment liquid penetrates into the inside of the recess. In particular, in the case where the hydrophobicity of the third end in the first region and the third region, which are regions near the opening of the recess, is greater than the hydrophobicity of the first end in the second region, which is a region on the bottom side of the recess, the tendency becomes significant. Therefore, in such a case, at least one of the following adjustments is preferably performed: a) reducing the surface tension of the second treatment liquid (for example, increasing the concentration of the additive); b) extending the supply time of the second treatment liquid; c) increasing the temperature of the second treatment liquid. Thus, in order to enable the second treatment liquid to penetrate into the second region, more preferably to enable the second treatment liquid to penetrate into the bottom of the recess in the second region, at least one of the surface tension, the supply time, and the temperature of the second treatment liquid is preferably adjusted. In addition, the supply time of the second treatment liquid in the present step is preferably longer than the supply time of the first treatment liquid in step B, and the temperature of the second treatment liquid in the present step is more preferably higher than the temperature of the first treatment liquid in step B.

[0245] For example, in the case where water is used as the liquid that reacts with the first end and ethanol is used as the additive, the concentration of the additive in the second treatment liquid is, for example, 0.1 to 99.9%, and is preferably 10 to 90%. In addition, regarding the concentration of the additive, a concentration can be exemplified that makes the contact angle of the second treatment liquid with respect to the second region whose surface is capped with the first end, and the contact angle of the second treatment liquid with respect to the first region and the third region whose surfaces are capped with the third end, each become 10 to 100°, and is preferably 10 to 90°. The concentration of the additive in the second treatment liquid in the present step is preferably higher than the concentration of the additive in the first treatment liquid in step B.

[0246] After the first end in the second region of the wafer 200 is selectively removed and replaced with the fifth end, the wafer 200 is lifted from the processing tank 710 by the moving mechanism, and placed on a placement table inside the second cleaning device 700. The wafer 200 placed on the placement table is carried out to the outside of the second cleaning device 700 by the carrying mechanism 850, and loaded into the wafer boat 217 via the carrying chamber 800.

[0247] (Wafer filling and wafer boat loading)

[0248] Then, the wafer 200 is filled in the wafer boat 217 and carried into the processing chamber 201 in the same steps as in the above first method.

[0249] (Pressure adjustment and temperature adjustment)

[0250] Then, the pressure and temperature in the processing chamber 201 are adjusted by the same steps as the pressure adjustment and temperature adjustment in the above-described first mode.

[0251] [Step F: Film formation step]

[0252] In this step, the wafer 200 is supplied with a raw material and an oxidizing agent as film formation agents. Thereby, a film is formed selectively in the second region. In this step, specifically, the following step fl and step f2 are executed in this order.

[0253] [Step fl]

[0254] After the end of the step E, the wafer 200, which is carried into the processing chamber 201 in the film formation apparatus 500 from the second cleaning apparatus 700, i.e., the wafer 200 after the fifth end is formed selectively in the second region, is supplied with a raw material. In this step, the wafer 200 can be supplied with a raw material by the same processing steps and processing conditions as the raw material supply in the step a0a of the above-described first mode. The raw material used in this step is sometimes referred to as a third raw material.

[0255] By supplying the wafer 200 with a raw material under the above-described processing conditions, at least a part of the molecular structure of the molecules constituting the raw material is selectively adsorbed to the second region in which the fifth end is formed, and thereby a sixth layer is formed selectively in the second region. At this time, the adsorption of at least a part of the molecular structure of the molecules constituting the raw material to the first and third regions is suppressed by the adsorption suppression effect of the third end formed in these regions (see (f) in Figure 9

[0256] In addition, as the raw material (third raw material) supplied to the wafer 200 in this step, one or more of the gases listed as examples of the raw material (first raw material) supplied to the wafer 200 in the step a0a of the first mode can be used. The third raw material can be the same as the first raw material, or can be different. In the case where a raw material different from the first raw material is used as the third raw material, a third raw material supply system (third raw material exposure system) configured to supply the third raw material is further provided. Like the above-described raw material supply system, the third raw material supply system is configured, for example, by a gas supply pipe connected to the nozzle 249a, an MFC, and a valve.

[0257] After the sixth layer is formed selectively in the second region of the wafer 200, the valve 243a is closed, and the supply of the raw material into the processing chamber 201 is stopped. Then, by the same processing steps and processing conditions as the purge in the step a0a described in the first mode, the gas-like substances and the like remaining in the processing chamber 201 are exhausted from the processing chamber 201.

[0258] [Step f2] ​

[0259] After the end of step fl, the wafer 200 in the processing chamber 201, i.e., the wafer 200 after the formation of the sixth layer in the second region selectively, is supplied with an oxidizing agent as a reactant. In this step, the wafer 200 can be supplied with the oxidizing agent by the same processing steps and processing conditions as those in the supply of the oxidizing agent in step aOb in the first mode. The oxidizing agent used in this step is sometimes referred to as a third reactant or a third oxidizing agent.

[0260] By supplying the wafer 200 with the oxidizing agent under the above processing conditions, at least a part of the sixth layer formed in the second region in step fl can be oxidized. Thus, in the second region, the seventh layer in which the sixth layer is oxidized and has OH terminals on the surface is formed.

[0261] In addition, as the oxidizing agent (third oxidizing agent) supplied to the wafer 200 in this step, one or more of the gases exemplified above as the oxidizing agent (first oxidizing agent) supplied to the wafer 200 in step aOb in the first mode can be used. The third oxidizing agent can be the same as the first oxidizing agent or different. In the case where the oxidizing agent different from the first oxidizing agent is used as the third oxidizing agent, a third oxidizing agent supply system (third oxidizing agent exposure system) configured to supply the third oxidizing agent is also provided. Like the above oxidizing agent supply system, the third oxidizing agent supply system is configured, for example, by a gas supply pipe connected to a nozzle 249b, an MFC, and a valve.

[0262] After the sixth layer formed in the second region of the wafer 200 is converted into the seventh layer, the valve 243b is closed, and the supply of the oxidizing agent into the processing chamber 201 is stopped. Then, by the same processing steps and processing conditions as those in the purging in step aOa in the first mode, the gaseous substances and the like remaining in the processing chamber 201 are exhausted from the processing chamber 201.

[0263] [Prescribed number of times]

[0264] By sequentially performing the above steps fl and f2 non-simultaneously n3 times (n3 is an integer of 1 or more), a film can be formed in the second region in such a manner that the film formation rate in the second region becomes greater than the film formation rate in the first region. In addition, a film can be formed in the second region in such a manner that the film formation rate in the second region becomes greater than the film formation rate in the third region. In other words, a film can be formed in the second region of the wafer 200 selectively (in (f) in the above description). Figure 10 In detail, a film can be formed in the second region on the inside (deep portion) side of the recess while suppressing the film formation in the first region and the third region on the opening side of the recess. The above cycle is preferably repeated a plurality of times until the film thickness of the film formed by laminating the seventh layers becomes a desired film thickness.

[0265] After the completion of Step F, the subsequent purge, atmospheric pressure recovery, wafer boat unloading, and wafer extraction are performed. The details are the same as those after Step A.

[0266] (2) Effects of the present embodiment

[0267] According to the present embodiment, one or more of the effects shown below can be obtained.

[0268] (a) In Step B, by removing the first end in the first region in such a manner that the density of the first end in the first region becomes lower than the density of the first end in the second region, film formation can be freely performed in these regions. For example, in Step F performed after Steps A and B, a film can be selectively formed in the second region compared to the first region.

[0269] (b) In Step B, by removing the first end in the third region in such a manner that the density of the first end in the third region becomes lower than the density of the first end in the second region, film formation can be freely performed in these regions. For example, in Step F performed after Steps A and B, a film can be selectively formed in the second region compared to the third region.

[0270] (c) In Step D, by supplying the wafer 200 after Step B with the second modifier, a third end is formed in the first region. Thus, a film can be more selectively formed in the second region compared to the first region.

[0271] (d) In Step E, by supplying the wafer 200 after Step D with the second treatment liquid containing a liquid that reacts with the first end and having a surface tension lower than the first treatment liquid, the first end in the second region is removed. In this way, by using the second treatment liquid having a surface tension lower than the first treatment liquid, the second treatment liquid can be made to permeate the second region (the bottom side of the recess). In the present embodiment, since the first end is more likely to react with the second treatment liquid compared to the third end, the first end in the second region can be reliably removed. By removing the first end that hinders the adsorption of the film formation agent, a film can be selectively formed in the second region in Step F.

[0272] In the case where the first end in the second region is a hydrophobic end, it is difficult to cause the second treatment liquid to infiltrate the second region. This tendency becomes significant in the case where the third end in the first region is a hydrophobic end, and becomes more significant in the case where the hydrophobicity of the third end in the first region is greater than the hydrophobicity of the first end in the second region. In the present mode, the case where the hydrophobicity of the third end (e.g., an alkyl end) in the first region (in detail, the first region and the third region) is greater than the hydrophobicity of the first end (e.g., an H end) in the second region is exemplified. In such a case, as a means of causing the second treatment liquid to infiltrate the second region, it is particularly effective to use the second treatment liquid having a surface tension smaller than the first treatment liquid.

[0273] (e) In step F, a film is formed in the second region in such a manner that the film formation rate in the second region becomes greater than the film formation rate in the first region by supplying a film formation agent to the wafer 200 after step D. Thereby, compared to the first region, a film can be selectively formed in the second region, and for example, the embedding property in the recess can be improved (e.g., generation of voids, seams is suppressed).

[0274] (3) Modified example

[0275] The substrate processing sequence in the present mode can be changed as in the following modified examples. These modified examples can be arbitrarily combined.

[0276] (Modified example 1)

[0277] In the above mode, an example in which the third end is formed in the first region and the third region in step D is described, but the present application is not limited thereto. For example, in step D, the third end can be formed only in the first region (see (d) in Figure 10 ).

[0278] In the present modified example, the same effects as in the above mode can be obtained. Further, according to the present modified example, in step F, film formation onto the upper surface of the recess is hindered, and film formation can be selectively performed only on the entire inner surface of the recess (see (f) in ​ ). Therefore, for example, the embedding property can be further improved.

[0279] (Modified example 2)

[0280] In the above mode, an example in which step E is performed before step F is performed is described. However, the present application is not limited to these aspects. For example, step F can be performed without performing step E after step D is performed.

[0281] In the present modification example, at least a part of the effects of the above-described mode can be obtained. In the execution of Step F, the first end in the second region is more likely to be detached from the wafer 200 than the third end in the first region, and thus even if Step E is omitted, the film can be selectively formed in the second region by selective breakage. In addition, the third end has a greater effect of hindering the adsorption of the film forming agent than the first end, and thus even if Step E is omitted, the film can be selectively formed in the second region. However, in order to improve the selectivity of film formation, it is preferable to perform Step E.

[0282] (Modification Example 3)

[0283] In the above-described mode, an example in which the wafer 200 on which Step E has been performed is supplied with the film forming agent is described. However, the present application is not limited to this mode. For example, the wafer 200 on which Step E has been performed can be supplied with the etching agent. In the present modification example, the same effects as those of the above-described mode can be obtained. That is, the second region can be subjected to selective etching treatment.

[0284] (Modification Example 4)

[0285] In the above-described mode, an example in which the third end formed in the first region and the third region and the first end formed in the second region are both ends that impart hydrophobicity to the top surface of the wafer 200 is described. However, the present application is not limited to this mode. For example, at least one of the first end and the third end can be an end that imparts hydrophobicity to the top surface of the wafer 200. In the present modification example, the same effects as those of the above-described mode can be obtained.

[0286] (Other Modes of the Present Application)

[0287] The above describes the modes of the present application. However, the present application is not limited to the above-described modes, and various modifications can be made without departing from the gist thereof.

[0288] For example, in the above-described mode, an example in which the first treatment liquid contains an additive that lowers the surface tension of the liquid is described. However, the present application is not limited to this mode. For example, depending on the liquid used, the first treatment liquid can contain an additive that increases the surface tension of the liquid. In the present mode, the same effects as those of the above-described mode can be obtained.

[0289] For example, in the above-described mode, a case where the prescribed element included in the raw material is Si is described as an example. However, the present application is not limited to this mode. For example, the prescribed element can also be a metal element such as titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), niobium (Nb), aluminum (Al), molybdenum (Mo), tungsten (W), germanium (Ge), or the like. In these cases, a metal-based oxide film such as a titanium oxide film (TiO film), a zirconium oxide film (ZrO film), a hafnium oxide film (HfO film), a tantalum oxide film (TaO film), a niobium oxide film (NbO film), an aluminum oxide film (AlO film), a molybdenum oxide film (MoO film), a tungsten oxide film (WO film), a germanium oxide film (GeO film), or the like is formed. The prescribed element included in the first raw material and the second raw material can also be different from each other, and the prescribed element included in the first raw material and the third raw material can also be different from each other. In this mode, the same effects as those of the above-described mode can also be obtained.

[0290] For example, in the above-described mode, a case where the oxide film is formed on the surface of the wafer 200 in the film formation process (step C, step F) is described as an example. However, the present application is not limited to these aspects. As the film selectively formed on the surface of the wafer 200, as long as it is a film that can be formed on the surface of the wafer 200 after step B, for example, it can also be a nitride film, a single film of Si, a metal element, or the like. For example, in a case where a nitride film is selectively formed as the film on the surface of the wafer 200, as the reactant (second reactant, third reactant) used in the film formation process, a nitriding agent (for example, NH3 gas or the like containing nitrogen gas) can be used instead of the oxidizing agent. In this mode, the same effects as those of the above-described mode can also be obtained.

[0291] In the above-described mode, an example where the film is formed using the batch substrate processing apparatus 100 that processes a plurality of substrates at a time is described. The present application is not limited to the above-described mode, and for example, it can also be appropriately applied to a case where the film is formed using a single substrate processing apparatus 100 that processes one or a few substrates at a time. In addition, in the above-described mode, an example where the film is formed using the substrate processing apparatus 100 having a heat wall type processing furnace is described. The present application is not limited to the above-described mode, and it can also be appropriately applied to a case where the film is formed using a substrate processing apparatus 100 having a cold wall type processing furnace.

[0292] In a case where these substrate processing apparatuses 100 are used, each process can also be performed with the same process steps and process conditions as those of the above-described mode and the modified example, and the same effects as those of the above-described mode and the modified example can be obtained.

[0293] The above-described mode and the modified example can be appropriately combined. The process steps and process conditions at this time can be set to be the same as those of the above-described mode and the modified example, for example.

Claims

1. A substrate processing method, comprising: (a) A process of preparing a substrate having a first region sealed by a first end and a second region sealed by the first end, wherein the first region constitutes the outer surface of a recess and is adjacent to the opening of the recess, and the second region constitutes the inner surface of the recess. and (b) A process of removing the first end in the first region by exposing the substrate to a first processing liquid containing a liquid that reacts with the first end, such that the density of the first end in the first region becomes less than the density of the first end in the second region.

2. The substrate processing method according to claim 1, wherein, The inner surface of the substrate provided in (a) further includes a third region located further toward the opening than the second region and sealed by the first end. In (b), the first end in the third region is removed in such a way that the density of the first end in the third region becomes less than the density of the first end in the second region.

3. The substrate processing method according to claim 1 or 2, wherein, The first treatment liquid contains an additive that causes a change in the surface tension of the liquid.

4. The substrate processing method according to claim 2 or 3, wherein, The surface tension of the first treatment liquid, the exposure time in the first treatment liquid, and the temperature of the first treatment liquid are adjusted in accordance with at least any one of (i), (ii), and (iii) below. (i) The distance from the opening to the position furthest from the opening in the third region; (ii) the width of the opening; (iii) The type of the first end.

5. The substrate processing method according to any one of claims 2 to 4, wherein, The third region is adjacent to the opening.

6. The substrate processing method according to any one of claims 1 to 5, wherein, In (b), the removed first end is replaced with a second end that is different from the first end.

7. The substrate processing method according to any one of claims 1 to 6, wherein, Also includes: (c) A process of forming a film in the first region by supplying a film-forming agent to the substrate after (b) such that the film-forming rate in the first region becomes greater than the film-forming rate in the second region.

8. The substrate processing method according to any one of claims 1 to 6, wherein, Also includes: (d) A process of forming a third end in the first region by supplying a second modifier to the substrate after (b).

9. The substrate processing method according to claim 8, wherein, Also includes: (e) A step of removing the first end of the second region by exposing the substrate after (d) to a second processing liquid, wherein the second processing liquid contains a liquid that reacts with the first end and has a lower surface tension than the first processing liquid.

10. The substrate processing method according to claim 8 or 9, wherein, Also includes: (f) A process of forming a film on the second region by supplying a film-forming agent to the substrate after (d) such that the film-forming rate of the second region becomes greater than that of the first region.

11. The substrate processing method according to claim 7, wherein, The first end prevents the film-forming agent from adsorbing onto the outermost surface of the substrate.

12. The substrate processing method according to claim 10, wherein, The first and third ends prevent the film-forming agent from adsorbing onto the outermost surface of the substrate. Compared to the first end, the third end has a greater effect in preventing the film-forming agent from adsorbing onto the outermost surface of the substrate.

13. The substrate processing method according to any one of claims 1 to 12, wherein, The first end is the end that imparts hydrophobicity to the outermost surface of the substrate.

14. The substrate processing method according to any one of claims 1 to 13, wherein, The liquid is a liquid of a compound whose molecule contains an OH terminus.

15. The substrate processing method according to any one of claims 1 to 14, wherein, The liquid that reacts with the first end is a liquid containing H2O or H2O2.

16. The substrate processing method according to any one of claims 1 to 15, wherein, (a) also includes: (a-1) The process of forming the first end in the first region and the second region by supplying the first modifier to the substrate.

17. A method for manufacturing a semiconductor device, comprising: (a) A process of providing a substrate having a first region sealed by a first end and a second region sealed by the first end, the first region forming an outer surface of a recess and adjacent to an opening of the recess, the second region forming an inner surface of the recess; and (b) A process of removing the first end in the first region by exposing the substrate to a first processing liquid containing a liquid that reacts with the first end, such that the density of the first end in the first region becomes less than the density of the first end in the second region.

18. A process article which, by means of a computer, causes a substrate processing apparatus to perform the following steps: (a) the step of providing a substrate having a first region sealed by a first end and a second region sealed by the first end, the first region forming an outer surface of a recess and adjacent to an opening of the recess, the second region forming an inner surface of the recess; and (b) The step of removing the first end in the first region by exposing the substrate to a first processing liquid containing a liquid that reacts with the first end, such that the density of the first end in the first region becomes less than the density of the first end in the second region.

19. A substrate processing apparatus, comprising: The first processing liquid exposure system is configured to expose the substrate to the first processing liquid. The control unit is configured to control the first processing liquid exposure system to perform the following process: by exposing the substrate having a first region sealed with a first end and a second region sealed with the first end to the first processing liquid containing a liquid that reacts with the first end, the first end in the first region is removed in such a way that the density of the first end in the first region becomes less than the density of the first end in the second region. The first region forms the outer surface of the recess and is adjacent to the opening of the recess, while the second region forms the inner surface of the recess.

20. The substrate processing apparatus according to claim 19, further comprising a first modifier supply system for supplying the first modifier to the substrate. The control unit is configured to control the first modifier supply system to perform the following process: supplying the first modifier to the substrate to form the first end in the first region and the second region.

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