Processing method, method of manufacturing semiconductor device, processing apparatus, and program

Abstract

To provide a technique capable of effectively adjusting a state of an inhibitor adsorbed on a surface of a substrate.SOLUTION: (a) a step of preparing a substrate having a first surface and a second surface, the first surface and the second surface having an inhibitor adsorbed thereon; and (b) a step of removing a part of the inhibitor adsorbed on the first surface and a part of the inhibitor adsorbed on the second surface by exposing the substrate to a treatment agent, and reducing or nullifying a film formation inhibition effect by the inhibitor remaining on the second surface while maintaining a film formation inhibition effect by the inhibitor remaining on the first surface.SELECTED DRAWING: Figure 4

Description

[Technical Field]

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

[0002] As one step in the manufacturing process of a semiconductor device, a process of adsorbing an inhibitor onto a specific surface among a plurality of surfaces of a substrate is sometimes carried out (see, for example, Patent Documents 1 to 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-106242 [Patent Document 2] Japanese Patent Publication No. 2020-155452 [Patent Document 3] Japanese Patent Publication No. 2020-155607 Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a technique that can effectively adjust the state of an inhibitor adsorbed on the surface of a substrate. [Means for solving the problem]

[0005] According to one aspect of the present disclosure, (a) providing a substrate having a first surface and a second surface, with an inhibitor adsorbed on said first surface and said second surface; (b) exposing the substrate to a treatment agent to remove a portion of the inhibitor adsorbed on the first surface and a portion of the inhibitor adsorbed on the second surface, thereby reducing or neutralizing the film formation inhibitory effect of the inhibitor remaining on the second surface while maintaining the film formation inhibitory effect of the inhibitor remaining on the first surface; The present invention provides a technique having: [Effects of the Invention]

[0006] According to the present disclosure, it is possible to effectively adjust the state of the inhibitor adsorbed on the surface of the substrate. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic diagram of a vertical processing furnace of a processing apparatus suitably used in one embodiment of the present disclosure, showing a processing furnace 202 portion in vertical cross section. [Figure 2] FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a processing apparatus suitably used in one embodiment of the present disclosure, and is a cross-sectional view of the processing furnace 202 portion taken along line AA in FIG. [Figure 3] FIG. 3 is a schematic configuration diagram of the controller 121 of the processing device suitably used in one embodiment of the present disclosure, and is a block diagram showing the control system of the controller 121. [Figure 4] Fig. 4(a) is a partial enlarged cross-sectional view showing a surface portion of a substrate having a first surface and a second surface according to an embodiment of the present disclosure. Fig. 4(b) is a partial enlarged cross-sectional view showing a surface portion of a substrate according to an embodiment of the present disclosure after being exposed to a modifying agent from the state of Fig. 4(a). Fig. 4(c) is a partial enlarged cross-sectional view showing a surface portion of a substrate according to an embodiment of the present disclosure after being exposed to a treatment agent from the state of Fig. 4(b). Fig. 4(d) is a partial enlarged cross-sectional view showing a surface portion of a substrate according to an embodiment of the present disclosure after being exposed to a film-forming agent from the state of Fig. 4(c). [Figure 5] Fig. 5(a) is a sequence diagram of a processing method according to one aspect of the present disclosure, in which steps A to C are performed in order without overlap. Fig. 5(b) is a sequence diagram of a processing method according to another aspect of the present disclosure, in which, after step A is performed, step B is performed with at least a partial overlap with step C. Fig. 5(c) is a sequence diagram of a processing method according to another aspect of the present disclosure, in which, after step A is performed, step B is performed with an initial overlap with step C. DETAILED DESCRIPTION OF THE INVENTION

[0008] <One aspect of the present disclosure> Hereinafter, one embodiment of the present disclosure will be described mainly with reference to Figures 1 to 3, 4(a) to 4(d), and 5(a). Note that the drawings used in the following description are all schematic, and the dimensional relationships between elements, the ratios of elements, etc. shown in the drawings do not necessarily match those in reality. Furthermore, the dimensional relationships between elements, the ratios of elements, etc. do not necessarily match between multiple drawings.

[0009] (1) Configuration of the processing device As shown in Fig. 1, the processing furnace 202 of the processing apparatus has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is installed vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gases with heat.

[0010] A reaction tube 203 is disposed concentrically with the heater 207 inside the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and has a cylindrical shape with a closed upper end and an open lower end. A manifold 209 is disposed concentrically with the reaction tube 203 below the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS) and has a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing member. The reaction tube 203 is installed vertically, similar to the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in the cylindrical hollow portion of the processing vessel. The processing chamber 201 is configured to be able to accommodate wafers 200 as substrates. In the processing chamber 201, processing of the wafers 200 is performed.

[0011] Nozzles 249a to 249c serving as first to third supply units are respectively provided in the processing chamber 201 so as to penetrate the sidewall of the manifold 209. The nozzles 249a to 249c are also referred to as first to third nozzles, respectively. The nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC. Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively. The nozzles 249a to 249c are different nozzles, and each of the nozzles 249a and 249c is provided adjacent to the nozzle 249b.

[0012] Gas supply pipes 232a-232c are provided with mass flow controllers (MFCs) 241a-241c, which are flow rate control devices (flow rate control parts), and valves 243a-243c, which are on-off valves, in order from the upstream side of the gas flow. Gas supply pipes 232d and 232f are connected to gas supply pipe 232a downstream of valve 243a. Gas supply pipes 232e and 232g are connected to gas supply pipe 232b downstream of valve 243b. Gas supply pipe 232h is connected to gas supply pipe 232c downstream of valve 243c. Gas supply pipes 232d-232h are provided with MFCs 241d-241h and valves 243d-243h, in order from the upstream side of the gas flow. Gas supply pipes 232a-232h are made of a metal material, such as SUS.

[0013] As shown in FIG. 2, the nozzles 249a to 249c are respectively provided in an annular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, extending from the lower part to the upper part of the inner wall of the reaction tube 203 and rising upward in the arrangement direction of the wafers 200. That is, the nozzles 249a to 249c are respectively provided in regions horizontally surrounding the wafer arrangement region on the sides of the wafer arrangement region where the wafers 200 are arranged, and extending along the wafer arrangement region. In a plan view, the nozzle 249b is disposed so as to face an exhaust port 231a (described later) on a straight line across the center of the wafer 200 in the processing chamber 201. The nozzles 249a and 249c are disposed so as to sandwich a line L passing through the nozzle 249b and the center of the exhaust port 231a along the inner wall of the reaction tube 203 (the outer periphery of the wafers 200) from both sides. The line L also passes through the nozzle 249b and the center of the wafer 200. In other words, the nozzle 249c can be said to be provided on the opposite side of the nozzle 249a across the line L. The nozzles 249a and 249c are arranged symmetrically with respect to the line L as the axis of symmetry. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. Each of the gas supply holes 250a to 250c opens to face (face) the exhaust port 231a in a plan view, and is able to supply gas toward the wafers 200. A plurality of the gas supply holes 250a to 250c are provided from the bottom to the top of the reaction tube 203.

[0014] The modifying agent is supplied from the gas supply pipe 232a into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.

[0015] From the gas supply pipe 232b, a raw material is supplied through the MFC 241b, the valve 243b, and the nozzle 249b into the processing chamber 201. The raw material is used as one of the film forming agents.

[0016] A reactant is supplied from the gas supply pipe 232c through the MFC 241c, the valve 243c, and the nozzle 249c into the processing chamber 201. The reactant is used as one of the film forming agents.

[0017] A catalyst is supplied from the gas supply pipe 232d through the MFC 241d, the valve 243d, the gas supply pipe 232a, and the nozzle 249a into the processing chamber 201. The catalyst is used as one of the film forming agents.

[0018] The processing agent is supplied from the gas supply pipe 232e into the processing chamber 201 via the MFC 241e, the valve 243e, the gas supply pipe 232b, and the nozzle 249b.

[0019] Inert gas is supplied from the gas supply pipes 232f to 232h through the MFCs 241f to 241h, the valves 243f to 243h, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c into the processing chamber 201. The inert gas acts as a purge gas, a carrier gas, a dilution gas, etc.

[0020] The modifying agent supply system (modifying agent exposure system) is mainly composed of the gas supply pipe 232a, MFC 241a, and valve 243a. The raw material supply system (raw material exposure system) is mainly composed of the gas supply pipe 232b, MFC 241b, and valve 243b. The reactant supply system (reactant exposure system) is mainly composed of the gas supply pipe 232c, MFC 241c, and valve 243c. The catalyst supply system (catalyst exposure system) is mainly composed of the gas supply pipe 232d, MFC 241d, and valve 243d. The treating agent supply system (treating agent exposure system) is mainly composed of the gas supply pipe 232e, MFC 241e, and valve 243e. The inert gas supply system (inert gas exposure system) is mainly composed of the gas supply pipes 232f-232h, MFCs 241f-241h, and valves 243f-243h. Each or all of the raw material supply system, reactant supply system, and catalyst supply system is also referred to as a film-forming agent supply system (film-forming agent exposure system).

[0021] Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which the valves 243a-243h, MFCs 241a-241h, etc. are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a-232h, and is configured so that the supply operation of various substances (various gases) into the gas supply pipes 232a-232h, i.e., the opening and closing operation of the valves 243a-243h and the flow rate adjustment operation by the MFCs 241a-241h, etc., are controlled by a controller 121, which will be described later. The integrated supply system 248 is configured as an integrated or separate integrated unit, and can be attached and detached to and from the gas supply pipes 232a-232h, etc., so that maintenance, replacement, expansion, etc. of the integrated supply system 248 can be performed on an integrated unit basis.

[0022] An exhaust port 231a for exhausting the atmosphere inside the processing chamber 201 is provided at the bottom of the sidewall of the reaction tube 203. As shown in FIG. 2, the exhaust port 231a is provided at a position facing (opposite) the nozzles 249a-249c (gas supply holes 250a-250c) across the wafer 200 in a plan view. The exhaust port 231a may be provided along the sidewall of the reaction tube 203 from the bottom to the top, i.e., along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246 serving as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 serving as a pressure detector (pressure detection unit) for detecting the pressure inside the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 serving as a pressure regulator (pressure adjustment unit). The APC valve 244 is configured to be able to evacuate and stop the evacuation of the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating, and further, to be able to adjust the pressure inside the processing chamber 201 by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating. An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

[0023] Below the manifold 209, a seal cap 219 is provided as a furnace port cover capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal material such as SUS and is formed in a disk shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a sealing member that abuts against the lower end of the manifold 209. Below the seal cap 219, a rotation mechanism 267 is provided to rotate the boat 217 (described later). A rotation shaft 255 of the rotation mechanism 267 penetrates the seal cap 219 and is connected to the boat 217. The rotation mechanism 267 is configured to rotate the boat 217, thereby rotating the wafers 200. The seal cap 219 is configured to be vertically raised and lowered by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers (transports) the wafers 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219, and functions as a device (preparation device) that prepares the wafers 200 in the processing chamber 201. When the inhibitor is adsorbed onto the surface of the wafer 200 in the processing chamber 201 as in this embodiment, each part of the processing device used for the process (such as a modifying agent supply system, a heating unit, and an exhaust system) may be included in the preparation device.

[0024] A shutter 219s is provided below the manifold 209 as a furnace port cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is removed from the processing chamber 201. The shutter 219s is made of a metal material such as SUS and has a disk shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that abuts against the lower end of the manifold 209. The opening and closing operation (lifting and lowering operation, rotating operation, etc.) of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

[0025] The boat 217 as a substrate support is configured to support a plurality of wafers 200, for example, 25 to 200 wafers 200, in a horizontal position and aligned vertically with their centers aligned, i.e., arranged at intervals, in multiple stages. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, heat insulating plates 218, also made of a heat-resistant material such as quartz or SiC, are supported in multiple stages.

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

[0027] As shown in FIG. 3, the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, such as a touch panel, is connected to the controller 121. An external storage device 123 can also be connected to the controller 121. The processing device may be configured to include one or more control units. That is, control for performing the processing sequence described below may be performed using one control unit or multiple control units. The multiple control units may be configured as a control system connected to each other via a wired or wireless communication network, and control for performing the processing sequence described below may be performed by the entire control system. In this specification, when the term "control section" is used, it may include one control section, multiple control sections, or a control system configured by multiple control sections.

[0028] The storage device 121c is configured with, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. Control programs for controlling the operation of the processing device, process recipes describing procedures and conditions for substrate processing (described later), etc., are readably recorded and stored in the storage device 121c. The process recipe is a combination of procedures for substrate processing (such as film formation processing) (described later) that are executed by the controller 121 to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, control program, etc. are collectively referred to simply as a program (program product). The process recipe is also simply referred to as a recipe. In this specification, the term "program" may refer to a recipe alone, a control program alone, or both. The RAM 121b is configured as a memory area (work area) for temporarily storing programs, data, etc. read by the CPU 121a.

[0029] The I / O port 121d is connected to the above-mentioned MFCs 241a to 241h, valves 243a to 243h, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, shutter opening / closing mechanism 115s, and the like.

[0030] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to input of an operation command from the input / output device 122. The CPU 121a is configured to control, in accordance with the contents of the read recipe, the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241h, the opening and closing operation of the valves 243a to 243h, the opening and closing operation of the APC valve 244 and the pressure adjustment operation by 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 heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, and the like.

[0031] The controller 121 can be configured by installing the above-mentioned program recorded and stored 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, or a semiconductor memory such as a USB memory or an SSD. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these will be collectively referred to as recording media. When the term recording media is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both. Note that the program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0032] (2) Treatment process An example of a method of processing a substrate (processing method) as one step in a semiconductor device manufacturing process (manufacturing method) using the processing apparatus described above, i.e., a processing sequence for adjusting the state of an inhibitor adsorbed on the surface of a wafer 200 as a substrate and then forming a film on part of the surface of the wafer 200, will be described mainly with reference to FIGS. 4(a) to 4(d) and 5(a). In the following description, the operation of each component constituting the processing apparatus is controlled by a controller 121. The processing apparatus will also be referred to as a substrate processing apparatus, a film formation processing apparatus, or a film formation apparatus. The processing method will also be referred to as a substrate processing method, a film formation processing method, or a film formation method.

[0033] In the processing sequence of this embodiment, (a) Step A of preparing a wafer 200 having a first surface and a second surface, with an inhibitor adsorbed on the first surface and the second surface; (b) Step B of exposing the wafer 200 to a processing agent to remove a portion of the inhibitor adsorbed on the first surface and a portion of the inhibitor adsorbed on the second surface, thereby reducing or nullifying the film formation inhibitory effect of the inhibitor remaining on the second surface while maintaining the film formation inhibitory effect of the inhibitor remaining on the first surface; Do the following.

[0034] In the following example, (c) A case will be described in which step C is further performed in which the wafer 200 after being exposed to the processing agent is exposed to a film-forming agent to form a film on the second surface.

[0035] In the following example, as shown in Figure 5(a), A case where steps A to C are performed in this order without overlapping will be described.

[0036] The term "wafer" used in this specification may refer to the wafer itself or to a laminate of the wafer and a predetermined layer or film formed on its surface. The term "surface of a wafer" used in this specification may refer to the surface of the wafer itself or to the surface of a predetermined layer or the like formed on the wafer. When described in this specification, "forming a predetermined layer on the surface of a wafer" may mean forming a predetermined layer directly on the surface of the wafer itself or forming a predetermined layer on a layer or the like formed on the wafer. When used in this specification, the term "substrate" is synonymous with the term "wafer".

[0037] The terms "agent" and "substance" used in this specification include at least one of gaseous and liquid substances. Liquid substances include mist-like substances. That is, each of the modifier, processing agent, and film-forming agent (raw material, reactant, catalyst) may contain a gaseous substance, a liquid substance such as a mist-like substance, or both.

[0038] (Wafer charge and boat load) When a plurality of wafers 200 are loaded into the boat 217 (wafer charge), the shutter 219s is moved by the shutter opening / closing mechanism 115s to open the lower end opening of the manifold 209 (shutter open). Thereafter, as shown in Fig. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into the processing chamber 201 (boat load). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.

[0039] 4(a), wafers 200 as substrates loaded into a boat 217 have a first material and a second material on their surfaces. The surface of the first material constitutes a first surface, and the surface of the second material constitutes a second surface. The first material and the second material are also referred to as a first base and a second base, respectively.

[0040] Here, the first surface contains an oxide, and the second surface contains a material different from this oxide (the oxide contained in the first surface). Also, the oxygen concentration of the first surface is higher than the oxygen concentration of the second surface. That is, the density of hydroxyl groups (OH groups) terminating the first surface is higher than the density of OH groups terminating the second surface.

[0041] The first surface may contain silicon (Si), and the second surface may contain at least one of Si and a metal, or may be Si-free. Alternatively, the first surface may contain Si and oxygen (O), and the second surface may contain Si and nitrogen (N). As exemplified below, the first surface and the second surface may each be made of any material as long as the above-mentioned condition is satisfied: the oxygen concentration of the first surface is higher than the oxygen concentration of the second surface, i.e., the density of OH groups terminating on the first surface is higher than the density of OH groups terminating on the second surface.

[0042] The first surface may be made of a material containing Si and O, such as silicon oxide (SiO), silicon oxynitride (SiON), silicon oxycarbide (SiOC), silicon oxycarbonitride (SiOCN), silicon boron oxynitride (SiBON), or silicon boron carbonate nitride (SiBCON). The first surface may be made of a material containing metal, Si, and O, such as aluminum silicon oxide (AlSiO), titanium silicon oxide (TiSiO), zirconium silicon oxide (ZrSiO), hafnium silicon oxide (HfSiO), or tantalum silicon oxide (TaSiO). The first surface may be made of a material containing metal and O, such as aluminum oxide (AlO), titanium oxide (TiO), zirconium oxide (ZrO), hafnium oxide (HfO), tantalum oxide (TaO), molybdenum oxide (MoO), zirconium aluminum oxide (ZrAlO), or hafnium aluminum oxide (HfAlO). These materials can also be called films, and for example, oxides can also be called oxide films.

[0043] The second surface may be formed of, for example, a material containing the same elements as the material forming the first surface but having a lower oxygen concentration than the material forming the first surface. The second surface may be formed of a material containing Si and N, such as silicon nitride (SiN), silicon carbonitride (SiCN), silicon boronitride (SiBN), or silicon boron carbonitride (SiBCN). The second surface may be formed of a material containing metal and N, such as aluminum nitride (AlN), titanium nitride (TiN), or tungsten nitride (WN). The second surface may be formed of a material containing a semiconductor element or a metal element, such as silicon (Si), silicon germanium (SiGe), tungsten (W), or molybdenum (Mo). These materials may also be referred to as films, and nitrides may be referred to as nitride films, for example.

[0044] (pressure and temperature regulation) After the boat loading is completed, the processing chamber 201, i.e., the space in which the wafers 200 are present, is evacuated (reduced pressure exhausted) by the vacuum pump 246 so that the interior of the processing chamber 201 is at a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. Furthermore, the wafers 200 inside the processing chamber 201 are heated by the heater 207 so that the processing temperature is at a desired processing temperature. At this time, the power supply to the heater 207 is feedback-controlled based on temperature information detected by the temperature sensor 263 so that the processing chamber 201 has a desired temperature distribution. Furthermore, the rotation mechanism 267 starts to rotate the wafers 200. The evacuation inside the processing chamber 201 and the heating and rotation of the wafers 200 are all continued at least until the processing of the wafers 200 is completed.

[0045] (Step A) The wafer 200 is then exposed to a modifying agent.

[0046] Specifically, the valve 243a is opened to allow the modifying agent to flow into the gas supply pipe 232a. The flow rate of the modifying agent is adjusted by the MFC 241a, and the modifying agent is supplied into the processing chamber 201 through the nozzle 249a and exhausted from the exhaust port 231a. At this time, the modifying agent is supplied to the wafer 200 from the side of the wafer 200, and the wafer 200 is exposed to the modifying agent (modifying agent supply, exposure). At this time, the valves 243f to 243h may be opened to supply an inert gas into the processing chamber 201 through each of the nozzles 249a to 249c.

[0047] By exposing the wafer 200 to the modifying agent under processing conditions described below, at least a portion of the molecular structure of the molecules constituting the modifying agent, i.e., the inhibitor contained in the modifying agent, can be adsorbed onto the first and second surfaces, as shown in Figure 4(b). The inhibitor adsorbed onto the surface of the wafer 200 functions to inhibit (suppress) the progress of the film formation reaction on the surface of the wafer 200, i.e., to extend the incubation time, in step C described below. This effect of the inhibitor is also called the film formation inhibition effect (reaction suppression effect, inhibitor effect).

[0048] This step is preferably carried out under at least one of the following conditions: the amount of inhibitor adsorbed to the first surface is greater than the amount of inhibitor adsorbed to the second surface; the density of inhibitor adsorbed to the first surface is greater than the density of inhibitor adsorbed to the second surface; and the coverage of the first surface by inhibitor adsorbed to the first surface is greater than the coverage of the second surface by inhibitor adsorbed to the second surface.

[0049] This step is preferably performed under conditions in which a continuous layer is formed by the inhibitor adsorbed on the first surface and a discontinuous layer is formed by the inhibitor adsorbed on the second surface. The layer formed by the inhibitor adsorbed on the surface of the wafer 200 is also referred to as an inhibitor layer.

[0050] After the inhibitor is adsorbed onto the first surface and the second surface, the valve 243a is closed to stop the supply of the modifying agent into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove gaseous substances remaining in the processing chamber 201. At this time, the valves 243f to 243h are opened to supply an inert gas into the processing chamber 201 through the nozzles 249a to 249c. The inert gas supplied from the nozzles 249a to 249c acts as a purge gas, thereby purging the processing chamber 201 (purging). Note that the processing temperature during purging in this step is preferably the same as the processing temperature during supply of the modifying agent.

[0051] In this manner, the wafer 200 having the first surface and the second surface and having the inhibitor adsorbed on the first surface and the second surface is prepared in the processing chamber 201.

[0052] The processing conditions for supplying the modifier in step A are as follows: Treatment temperature: room temperature (25°C) to 500°C, preferably 25 to 250°C Treatment pressure: 5 to 2000 Pa, preferably 10 to 1000 Pa Processing time: 1 second to 120 minutes, preferably 30 seconds to 60 minutes Modifier supply flow rate: 0.001 to 3 slm, preferably 0.001 to 0.5 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm is exemplified.

[0053] In this specification, when a numerical range such as "25 to 500°C" is expressed, both the lower and upper limits are included in the range. For example, "25 to 500°C" means "25°C or higher and 500°C or lower." The same applies to other numerical ranges. In this specification, the processing temperature refers to the temperature of the wafer 200 or the temperature inside the processing chamber 201, and the processing pressure refers to the pressure inside the processing chamber 201. The processing time refers to the time the processing continues. In addition, when the supply flow rate includes 0 slm, 0 slm means that the substance (gas) is not supplied. These also apply to the following explanations.

[0054] The modifier may be, for example, a substance containing at least one of a hydrocarbon group and an amino group, and / or a fluorine (F)-containing substance. When both substances are used, it is preferable to first supply the substance containing at least one of a hydrocarbon group and an amino group, and then supply the F-containing substance after purging. When the substances exemplified below are used, the first and second surfaces are terminated with hydrocarbon groups such as alkyl groups, hydrogen (H), or F, and hydrocarbon group terminations such as alkyl group terminations, H terminations, F terminations, etc. function as inhibitors.

[0055] For example, the modifier may be a substance in which hydrogen (H) and an amino group are bonded to silicon, i.e., an aminosilane, such as tetrakis(dimethylamino)silane (Si[N(CH3)2]4), tris(dimethylamino)silane (Si[N(CH3)2]3H), bis(diethylamino)silane (Si[N(C2H5)2]2H2), bis(tertiarybutylamino)silane (SiH2[NH(C4H9)]2), (diisobutylamino)silane (SiH3[N(C4H9)2]), or (diisopropylamino)silane (SiH3[N(C3H7)2]).

[0056] Furthermore, for example, as a modifier, 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), or (dipropylamino)trimethylsilane ((C3H7)2NSi(CH3)3), can be used.

[0057] Furthermore, for example, fluorine (F2), nitrogen trifluoride (NF3), chlorine trifluoride (ClF3), chlorine fluoride (ClF), hydrogen fluoride (HF), or the like can be used as the modifier.

[0058] As the modifier, one or more of these can be used.

[0059] As the inert gas, nitrogen (N2) gas or a rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas can be used. One or more of these can be used as the inert gas. This also applies to each step described below.

[0060] (Step B) After step A is completed, the wafer 200 is exposed to a treatment agent.

[0061] Specifically, the valve 243e is opened to allow the processing agent to flow into the gas supply pipe 232e. The processing agent is adjusted in flow rate by the MFC 241e, supplied into the processing chamber 201 via the nozzle 249b, and exhausted from the exhaust port 231a. At this time, the processing agent is supplied onto the wafer 200 from the side of the wafer 200, and the wafer 200 is exposed to the processing agent (processing agent supply, exposure). At this time, the valves 243f to 243h may be opened to supply an inert gas into the processing chamber 201 via the nozzles 249a to 249c, respectively.

[0062] By exposing the wafer 200 to the treatment agent under the processing conditions described below, it is possible to remove a portion of the inhibitor adsorbed on the first surface and a portion of the inhibitor adsorbed on the second surface, as shown in FIG. 4(c). The dashed line in FIG. 4(c) schematically indicates the removal of the inhibitor. FIG. 4(c) shows an example in which the amount of inhibitor adsorbed on the first surface and the amount of inhibitor adsorbed on the second surface are similar, i.e., an example in which a portion of the inhibitor is non-selectively removed from each of the first and second surfaces. This non-selective removal makes it possible to reduce or neutralize the film formation inhibitory effect of the inhibitor remaining on the second surface while maintaining the film formation inhibitory effect of the inhibitor remaining on the first surface. Note that in FIG. 4(c), the amount of inhibitor remaining on the second surface is much less than the amount of inhibitor remaining on the first surface. Therefore, at first glance, it appears that the inhibitor adsorbed on the second surface has been selectively removed, but since the amount of inhibitor removed from the second surface is not greater than the amount of inhibitor removed from the first surface, this does not constitute selective removal, but rather non-selective removal.

[0063] In this step, it is preferable that the amount of inhibitor adsorbed onto the first surface that is removed is equal to or greater than the amount of inhibitor adsorbed onto the second surface that is removed, and it is even more preferable that the amount is greater than the amount of inhibitor adsorbed onto the second surface that is removed.

[0064] After a portion of the inhibitor is removed from each of the first surface and the second surface, the valve 243e is closed to stop the supply of the processing agent into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 using the same processing procedures and conditions as those used for purging in step A. Note that the processing temperature during purging in this step is preferably the same as the processing temperature during supply of the processing agent.

[0065] The processing conditions when supplying the processing agent in step B are as follows: Treatment temperature: room temperature (25°C) to 600°C, preferably 50 to 400°C Treatment pressure: 1 to 105,000 Pa, preferably 10 to 10,000 Pa Treatment time: 1 to 10,000 seconds, preferably 5 to 3,600 seconds Treatment agent supply flow rate: 0.01 to 10 slm, preferably 0.1 to 5 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm is exemplified.

[0066] Examples of the treatment agent that can be used include nitrogen (N)-containing substances, hydrogen (H)-containing substances, oxygen (O)-containing substances, fluorine (F)-containing substances, and chlorine (Cl)-containing substances. Examples of the treatment agent that can be used include N- and H-containing substances, H- and O-containing substances, H- and F-containing substances, N- and F-containing substances, Cl- and F-containing substances, F-, N-, and O-containing substances, H- and Cl-containing substances, and Cl- and Si-containing substances. A catalyst that can be used in step C, which will be described later, may be added to the treatment agent. The addition of a catalyst can enhance the action of the H- and O-containing substances as a treatment agent.

[0067] Examples of N- and H-containing substances include hydrogen nitrides such as ammonia (NH), hydrazine (N2H4), and diazene (N2H2). Examples of H- and O-containing substances include water (H2O), hydrogen peroxide (H2O2), and the like. Examples of O-containing substances include oxygen (O2), ozone (O3), and the like. Examples of H- and F-containing substances include hydrogen fluoride (HF), and the like. Examples of F-containing substances include fluorine (F2), and the like. Examples of N- and F-containing substances include nitrogen trifluoride (NF3), and the like. Examples of Cl- and F-containing substances include chlorine trifluoride (ClF3), chlorine fluoride (ClF), and the like. Examples of F-, N-, and O-containing substances include nitrosyl fluoride (FNO), and the like. Examples of H- and Cl-containing substances include hydrogen chloride (HCl), and the like. Examples of Cl-containing substances include chlorine (Cl2), and the like. Examples of Cl- and Si-containing substances that can be used include hexachlorodisilane (Si2Cl6), tetrachlorosilane (SiCl4), trichlorosilane (SiHCl3), dichlorosilane (SiH2Cl2), monochlorosilane (SiH3Cl), bis(trichlorosilyl)methane ((SiCl3)2CH2), 1,2-bis(trichlorosilyl)ethane ((SiCl3)2C2H4), hexachlorodisiloxane (Cl3Si-O-SiCl3), and octachlorotrisiloxane (Cl3Si-O-SiCl2-O-SiCl3).

[0068] As the treatment agent, one or more of these can be used.

[0069] (Step C) After step B is completed, the following steps C1 and C2 are performed to expose the wafer 200 to the film-forming agent.

[0070] [Step C1] In this step, the wafer 200 is exposed to a source material as a film forming agent.

[0071] Specifically, valve 243b is opened to allow the raw material to flow into gas supply pipe 232b. The raw material is adjusted in flow rate by MFC 241b, supplied into processing chamber 201 via nozzle 249b, mixed within processing chamber 201, and exhausted from exhaust port 231a. At this time, the raw material is supplied to wafer 200 from the side of wafer 200, exposing wafer 200 to the raw material (raw material supply, exposure). At this time, valve 243d may be opened to allow a catalyst to flow into gas supply pipe 232d, supplying the raw material and catalyst to wafer 200 and exposing wafer 200 to the raw material and catalyst. At this time, valves 243f to 243h may be opened to supply an inert gas into processing chamber 201 via nozzles 249a to 249c, respectively.

[0072] By exposing wafer 200 to the raw material under processing conditions described below, it is possible to selectively adsorb at least a portion of the molecular structure of the molecules constituting the raw material onto the second surface while suppressing adsorption of at least a portion of the molecular structure of the molecules constituting the raw material onto the first surface. As a result, a first layer is selectively formed on the second surface. The first layer contains at least a portion of the molecular structure of the molecules constituting the raw material, which is a residue of the raw material. In other words, the first layer contains at least a portion of the atoms constituting the raw material.

[0073] In this step, at least a portion of the molecular structure of the molecules constituting the raw material may be adsorbed to a portion of the first surface of the wafer 200, but the amount of adsorption is small, and the amount of adsorption to the second surface of the wafer 200 is overwhelmingly greater. Such selective (preferential) adsorption is possible because in step B, the state of the inhibitor adsorbed to the surface of the wafer 200 is effectively adjusted, and the film formation inhibitory effect of the inhibitor remaining on the first surface is maintained while the film formation inhibitory effect of the inhibitor remaining on the second surface is reduced or neutralized.

[0074] After the first layer is selectively formed on the second surface of the wafer 200, the valve 243b is closed to stop the supply of raw materials into the processing chamber 201. If a catalyst has been supplied together with the raw materials, the valve 243d is closed to stop the supply of the catalyst into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 (purging) using the same processing procedures and conditions as those for purging in step A. Note that the processing temperature when purging in this step is preferably the same as the processing temperature when supplying the raw materials.

[0075] The processing conditions for supplying the raw material in step C1 are as follows: Treatment temperature: 300 to 800°C, preferably 400 to 650°C Treatment pressure: 1 to 2000 Pa, preferably 1 to 1333 Pa Treatment time: 1 to 180 seconds, preferably 10 to 120 seconds Raw material supply flow rate: 0.001 to 2 slm, preferably 0.01 to 1 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm is exemplified.

[0076] The processing conditions for supplying the raw material and catalyst in step C1 are as follows: Treatment temperature: room temperature (25°C) to 200°C, preferably 25 to 150°C Treatment pressure: 13 to 2666 Pa, preferably 13 to 1333 Pa Treatment time: 1 to 90 seconds, preferably 1 to 60 seconds Raw material supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm Catalyst supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm is exemplified.

[0077] As the raw material, for example, a silicon (Si)-containing substance can be used.

[0078] For example, as raw materials, substances containing Si and a chloro group (Cl), i.e., chlorosilanes, such as monochlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), tetrachlorosilane (SiCl4), hexachlorodisilane (Si2Cl6), and octachlorotrisilane (Si3Cl8), can be used.

[0079] Furthermore, for example, materials containing Si, chloro groups (Cl), and hydrocarbon groups, such as 1,1,3,3-tetrachloro-1,3-disilacyclobutane (C2H4Cl4Si2), 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH3)2Si2Cl4), 1,2-dichloro-1,1,2,2-tetramethyldisilane ((CH3)4Si2Cl2), bis(trichlorosilyl)methane ((SiCl3)2CH2), and 1,2-bis(trichlorosilyl)ethane ((SiCl3)2C2H4), i.e., alkylchlorosilanes and alkylenechlorosilanes, can be used as raw materials.

[0080] Furthermore, for example, materials containing Si and a fluoro group (F), such as tetrafluorosilane (SiF), difluorosilane (SiH2F2), tetrabromosilane (SiBr4), dibromosilane (SiH2Br2), tetraiodosilane (SiI4), and diiodosilane (SiH2I2), materials containing Si and a bromo group (Br), and materials containing Si and an iodo group (I), i.e., fluorosilane, bromosilane, and iodosilane, can be used as raw materials. In addition, materials containing siloxane bonds and a chloro group (Cl), such as hexachlorodisiloxane (Cl3Si-O-SiCl3) and octachlorotrisiloxane (Cl3Si-O-SiCl2-O-SiCl3), can also be used as raw materials.

[0081] As the raw material, one or more of these can be used.

[0082] As the catalyst, for example, a substance containing an amino group can be used.

[0083] For example, the catalyst may be pyridine (C5H5N), aminopyridine (C5H6N2), picoline (C6H7N), lutidine (C7H9N), pyrimidine (C4H4N2), quinoline (C9H7N), piperazine (C4H 10 N2), piperidine (CH 11 Cyclic amines such as triethylamine ((C2H5)3N), diethylamine ((C2H5)2NH), monoethylamine ((C2H5)NH2), trimethylamine ((CH3)3N), dimethylamine ((CH3)2NH), monomethylamine ((CH3)NH2) can be used as catalysts.

[0084] One or more of these can be used as the catalyst. This also applies to step C2 described later.

[0085] [Step C2] In this step, the wafer 200 is exposed to a reactant as a film-forming agent.

[0086] Specifically, valve 243c is opened to allow reactants to flow into gas supply pipe 232c. The reactants are adjusted in flow rate by MFC 241c, supplied into processing chamber 201 via nozzle 249c, mixed within processing chamber 201, and exhausted through exhaust port 231a. At this time, the reactants are supplied to wafer 200 from the side of wafer 200, exposing wafer 200 to the reactants (reactant supply, exposure). At this time, valve 243d may be opened to allow a catalyst to flow into gas supply pipe 232d, supplying the reactants and catalyst to wafer 200 and exposing wafer 200 to the reactants and catalyst. At this time, valves 243f to 243h may be opened to supply an inert gas into processing chamber 201 via nozzles 249a to 249c, respectively.

[0087] By exposing the wafer 200 to a reactant under processing conditions described below, at least a portion of the first layer formed on the second surface of the wafer 200 in step C1 can be reacted with the reactant to convert the first layer into a second layer. For example, if the reactant contains an N-containing substance, at least a portion of the first layer can be nitrided to convert the first layer into a second layer containing Si and N, i.e., a silicon nitride layer (SiN layer). For example, if the reactant contains an O-containing substance, at least a portion of the first layer can be oxidized to convert the first layer into a layer containing Si and O, i.e., a silicon oxide layer (SiO layer). For example, if the reactant contains an N-containing substance and an O-containing substance, at least a portion of the first layer can be nitrided and oxidized to convert the first layer into a second layer containing Si, O, and N, i.e., a silicon oxynitride layer (SiON layer). When using the above-mentioned raw materials, the SiN layer may further contain C or O, and the SiO layer or SiON layer may further contain C. At this time, the first surface is covered with an inhibitor, and the reaction between the first surface and the reactant (nitridation or oxidation of the first surface) can be suppressed by the reaction suppressing effect of the inhibitor.

[0088] After the first layer formed on the second surface of wafer 200 is transformed into the second layer, valve 243c is closed to stop the supply of reactants into processing chamber 201. If a catalyst has been supplied together with the reactants, valve 243d is closed to stop the supply of catalyst into processing chamber 201. Then, gaseous substances remaining in processing chamber 201 are removed from processing chamber 201 (purging) using the same processing procedure and processing conditions as those for purging in step A. Note that the processing temperature when purging in this step is preferably the same as the processing temperature when supplying the reactants.

[0089] The processing conditions for supplying the reactants in step C2 are as follows: Treatment temperature: 300 to 800°C, preferably 400 to 650°C Treatment pressure: 1 to 4000 Pa, preferably 1 to 1333 Pa Treatment time: 1 to 180 seconds, preferably 10 to 120 seconds Reactant supply flow rate: 0.01 to 20 slm, preferably 0.01 to 10 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm is exemplified.

[0090] The process conditions for supplying the reactants and catalyst in step C2 are as follows: Treatment temperature: room temperature (25°C) to 200°C, preferably 25 to 150°C Treatment pressure: 13 to 2666 Pa, preferably 13 to 1333 Pa Treatment time: 1 to 90 seconds, preferably 1 to 60 seconds Reactant supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm Catalyst supply flow rate: 0.001 to 2 slm, preferably 0.001 to 1 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm is exemplified.

[0091] As the reactant, for example, an N-containing substance, ie, a nitriding agent, an O-containing substance, ie, an oxidizing agent, or the like can be used.

[0092] For example, as a reactant (nitriding agent), N- and H-containing substances such as NH3, N2H2, N2H4, and N3H8, i.e., hydrogen nitride, can be used.

[0093] Furthermore, for example, as a reactant (oxidizing agent), H and O-containing substances such as H2O, H2O2, hydrogen (H2) + O2, H2 + O3, etc. In this case, deuterium (D2) can also be used instead of H2.

[0094] In this specification, a combined description such as "H2+O2" means a mixture of H2 and O2. When supplying a mixture, the two substances may be mixed (premixed) in a supply pipe and then supplied into the processing chamber 201, or the two substances may be supplied separately from different supply pipes into the processing chamber 201 and mixed (postmixed) in the processing chamber 201.

[0095] Furthermore, for example, reactants (oxidizing agents) that can be used include O-containing substances such as O2, O3, nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), carbon monoxide (CO), and carbon dioxide (CO2).

[0096] One or more of these can be used as reactants.

[0097] As the catalyst, for example, the same substances as the various catalysts exemplified in step C1 above can be used.

[0098] [Perform the specified number of times] By performing a cycle including the above-described steps C1 and C2 a predetermined number of times (n times, where n is an integer of 1 or greater), a film can be formed on the second surface, as shown in FIG. 4(d). Using the above-described Si-containing material as a source material and the above-described nitriding agent as a reactant, a silicon nitride film (SiN film), a silicon carbonitride film (SiCN film), a silicon oxynitride film (SiON film), or the like can be formed on the second surface. Using the above-described Si-containing material as a source material and the above-described oxidizing agent as a reactant, a silicon oxide film (SiO film), a silicon oxycarbide film (SiOC film), or the like can be formed on the second surface. Using the above-described Si-containing material as a source material and the above-described nitriding agent and oxidizing agent as reactants, a silicon oxynitride film (SiON film), a silicon oxycarbonitride film (SiOCN film), or the like can be formed on the second surface. It is preferable to repeat the above-described cycle multiple times. That is, it is preferable to make the thickness of the second layer formed per cycle thinner than the desired film thickness, and to repeat the above-described cycle multiple times until the thickness of the film formed by stacking the second layer reaches the predetermined thickness. Even when the above-described cycle is repeated multiple times, the first surface remains covered with the inhibitor, and the film formation inhibiting effect of the inhibitor can suppress the formation of a film on the first surface.

[0099] (After purging and atmospheric pressure recovery) After step C is completed, an inert gas is supplied as a purge gas from each of the nozzles 249a to 249c into the processing chamber 201 and exhausted from the exhaust port 231a. This purges the processing chamber 201, and gases and reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (after-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure return).

[0100] (Boat unloading and wafer discharge) Thereafter, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafers 200, supported by the boat 217, are unloaded from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). After the boat unloading, the shutter 219s is moved, and the opening at the lower end of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). After being unloaded to the outside of the reaction tube 203, the processed wafers 200 are removed from the boat 217 (wafer discharge).

[0101] It is preferable to perform steps A to C in the same processing chamber (in-situ). If a series of processes is performed in-situ, the wafer 200 is not exposed to the atmosphere during the process, and the wafer 200 can be processed consistently while being kept under vacuum, enabling stable processing.

[0102] (3) Effects of this mode According to this aspect, one or more of the following effects can be obtained.

[0103] (a) In step B, a substrate having inhibitors adsorbed on its first and second surfaces is exposed to a treatment agent to remove a portion of the inhibitor adsorbed on the first surface and a portion of the inhibitor adsorbed on the second surface. That is, step B does not selectively remove the inhibitor adsorbed on the second surface, but rather allows for the removal of a portion of the inhibitor adsorbed on the first surface and a portion of the inhibitor adsorbed on the second surface. This relaxes the restrictions on the treatment conditions for removing the inhibitor in step B, allowing for greater flexibility in the treatment conditions.

[0104] By allowing flexibility in the processing conditions in step B, the processing temperature for removing a portion of the inhibitor in step B can be set to the same temperature as the processing temperature in the steps performed before and / or after step B. This eliminates the need for waiting time required for temperature adjustment, making it possible to avoid a decrease in productivity throughout the entire process.

[0105] Furthermore, by allowing flexibility in the processing conditions in step B, it becomes possible to remove (select) inhibitors with weak adsorption power on the first surface in advance from the first surface before performing step C. This reduces the amount of inhibitors that desorb from the first surface during the performance of step C, and as a result, it becomes possible to reduce the amount of impurities caused by inhibitors that are contained in the film formed in step C.

[0106] Furthermore, by allowing flexibility in the processing conditions in step B, it becomes possible to gently remove the inhibitor adsorbed on the second surface while suppressing damage to the second surface in step B. This makes it possible to properly maintain the state of the second surface after performing step B and improve the interfacial properties between the second surface and the film formed on the second surface in step C.

[0107] Furthermore, by allowing flexibility in the processing conditions in step B, it becomes possible to appropriately weaken the adsorption force of the inhibitor adsorbed on the first surface in step B. This may make it unnecessary to perform a reset step to remove the inhibitor remaining on the first surface after performing step C. Furthermore, even if a reset step is performed, it can be performed in a short time. As a result, it becomes possible to avoid a decrease in productivity throughout the entire process.

[0108] (b) In step B, it is possible to effectively adjust the state of the inhibitor adsorbed on each of the first and second surfaces. That is, in step B, rather than selectively removing the inhibitor adsorbed on the second surface, it is possible to allow partial removal of the inhibitor adsorbed on the first surface and partial removal of the inhibitor adsorbed on the second surface, while maintaining the film formation inhibitory effect of the inhibitor remaining on the first surface and reducing or neutralizing the film formation inhibitory effect of the inhibitor remaining on the second surface.

[0109] As a result, in step C, the incubation time on the first surface can be lengthened while the incubation time on the second surface can be shortened or eliminated, enabling selective film formation on the second surface. Furthermore, in step C, it is possible to improve the in-plane film thickness uniformity of the film formed on the second surface, improve surface roughness, and improve processing productivity. Note that surface roughness refers to the difference in height of the film surface within the substrate surface or any target surface, and the smaller the value, the smoother the surface. In this specification, improving (improving) surface roughness means that the difference in height of the film surface is reduced and the smoothness is improved (improved).

[0110] (c) By using a treatment agent used in step B that contains at least one of an N-containing substance, an H-containing substance, an O-containing substance, an F-containing substance, and a Cl-containing substance, step B can effectively maintain the film formation inhibitory effect of the inhibitor remaining on the first surface and reduce or neutralize the film formation inhibitory effect of the inhibitor remaining on the second surface.

[0111] Furthermore, by using the treatment agent used in step B containing at least one of an N- and H-containing substance, an H- and O-containing substance, an H- and F-containing substance, an N- and F-containing substance, a Cl- and F-containing substance, an F-, N- and O-containing substance, an H- and Cl-containing substance, and a Cl- and Si-containing substance, step B can more effectively maintain the film-formation inhibitory effect of the inhibitor remaining on the first surface and reduce or neutralize the film-formation inhibitory effect of the inhibitor remaining on the second surface.

[0112] Furthermore, if the treatment agent used in step B contains an H- and O-containing substance, for example, H2O or H2O2, step B can more effectively maintain the film-formation inhibitory effect of the inhibitor remaining on the first surface and reduce or neutralize the film-formation inhibitory effect of the inhibitor remaining on the second surface.

[0113] (d) By having the first surface contain an oxide and the second surface contain a material different from this oxide, in step B it is possible to effectively maintain the film formation inhibitory effect of the inhibitor remaining on the first surface and reduce or neutralize the film formation inhibitory effect of the inhibitor remaining on the second surface.

[0114] Furthermore, since the oxygen concentration on the first surface is higher than the oxygen concentration on the second surface, i.e., the density of OH groups terminating on the first surface is higher than the density of OH groups terminating on the second surface, step B can more effectively maintain the film formation inhibitory effect of the inhibitor remaining on the first surface and reduce or neutralize the film formation inhibitory effect of the inhibitor remaining on the second surface.

[0115] Furthermore, since the first surface contains Si and the second surface contains at least one of Si and a metal or does not contain Si, step B can more effectively maintain the film formation inhibitory effect of the inhibitor remaining on the first surface and reduce or neutralize the film formation inhibitory effect of the inhibitor remaining on the second surface.

[0116] (e) In step A, a substrate having a first surface and a second surface is exposed to a modifier, thereby causing the inhibitor contained in the modifier to be adsorbed onto each of the first surface and the second surface. That is, in step A, the inhibitor is not selectively adsorbed onto the first surface, but rather adsorption of the inhibitor onto the first surface and adsorption of the inhibitor onto the second surface are allowed. This relaxes the restrictions on the treatment conditions for adsorbing the inhibitor in step A, allowing for greater flexibility in the treatment conditions.

[0117] By allowing flexibility in the treatment conditions in step A, the treatment temperature for adsorbing the inhibitor in step A can be set to the same temperature as the treatment temperature in the steps performed before and / or after step A. This eliminates the need for waiting time for temperature adjustment, making it possible to avoid a decrease in productivity throughout the entire process.

[0118] (f) By performing step A under at least one of the following conditions: the amount of inhibitor adsorbed on the first surface is greater than the amount of inhibitor adsorbed on the second surface; the density of the inhibitor adsorbed on the first surface is greater than the density of the inhibitor adsorbed on the second surface; and the coverage of the first surface by the inhibitor adsorbed on the first surface is greater than the coverage of the second surface by the inhibitor adsorbed on the second surface, step B can effectively maintain the film formation inhibitory effect of the inhibitor remaining on the first surface and reduce or neutralize the film formation inhibitory effect of the inhibitor remaining on the second surface.

[0119] Furthermore, by performing step A under conditions in which a continuous layer is formed by the inhibitor adsorbed to the first surface and a discontinuous layer is formed by the inhibitor adsorbed to the second surface, it becomes possible to effectively maintain the film formation inhibitory effect of the inhibitor remaining on the first surface and reduce or neutralize the film formation inhibitory effect of the inhibitor remaining on the second surface in step B.

[0120] (g) In step B, by setting the amount of inhibitor adsorbed on the first surface to be removed equal to or greater than the amount of inhibitor adsorbed on the second surface to be removed, it becomes possible to further relax the restrictions on the treatment conditions in step B and allow greater flexibility in the treatment conditions in step B. This makes it possible to more effectively achieve the above-mentioned effects that can be obtained by allowing greater flexibility in the treatment conditions in step B.

[0121] Furthermore, by making the amount of inhibitor adsorbed on the first surface removed in step B greater than the amount of inhibitor adsorbed on the second surface removed, it becomes possible to further relax the restrictions on the treatment conditions in step B and provide greater flexibility in the treatment conditions in step B. This makes it possible to more effectively achieve the above-mentioned effects that can be obtained by providing greater flexibility in the treatment conditions in step B.

[0122] (h) In step C, by exposing the substrate after exposure to the treatment agent to a film-forming agent, it is possible to selectively form a film on the second surface while suppressing the formation of a film on the first surface.

[0123] (i) The above-mentioned effects can be similarly obtained when a predetermined substance is arbitrarily selected from the various modifiers, treatment agents, film-forming agents, and inert gases mentioned above.

[0124] <Other Aspects of the Present Disclosure> Although the embodiments of the present disclosure have been specifically described above, the present disclosure is not limited to the above embodiments and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0125] For example, the exposure of the substrate to the processing agent in step B is not limited to the case where the processing agent is supplied to the substrate in a gaseous state. For example, the exposure of the substrate to the processing agent may be performed by exposing the substrate to the atmosphere, or by exposing the substrate to a liquid processing agent, for example, by immersing the substrate in the liquid processing agent. That is, step B and steps A and C may be performed in different spaces (ex-situ).

[0126] In step B, the processing conditions for exposing the substrate to the atmosphere are as follows: Processing temperature: room temperature (25°C) Processing pressure: atmospheric pressure Processing time: 1 to 600,000 seconds, preferably 600 to 43,200 seconds is exemplified.

[0127] In step B, the processing conditions for exposing the substrate to the liquid processing agent are as follows: Treatment time: 1 to 600 seconds, preferably 1 to 120 seconds is exemplified.

[0128] The liquid treatment agent may be, for example, water, pure water, ultrapure water, etc. Pure water and ultrapure water include RO water, deionized water, distilled water, etc.

[0129] In these embodiments, the same effects as those in the above-mentioned embodiment can be obtained.

[0130] Furthermore, for example, the timing of performing steps A to C is not limited to the above-described embodiment in which each step is performed sequentially without overlapping. For example, as shown in FIG. 5(b), after performing step A, step B may be performed so that it at least partially overlaps with step C. For example, as shown in FIG. 5(c), after performing step A, step B may be performed so that it overlaps with step C at the beginning of step C. That is, when performing steps A to C, an overlap period T may be provided in which steps B and C are performed in parallel. In these cases, the film-forming agent includes a treatment agent. Specifically, the film-forming agent supplied during the overlap period T, i.e., at least one of the raw material and the reactant, acts as the treatment agent. Note that in addition to at least one of the raw material and the reactant, a catalyst may also act as the treatment agent. Furthermore, the catalyst may promote the action of at least one of the raw material and the reactant as the treatment agent.

[0131] The processing conditions for supplying raw materials in step C1 during the overlap period T are as follows: Treatment temperature: 300 to 800°C, preferably 400 to 650°C Treatment pressure: 1 to 3000 Pa, preferably 1 to 2000 Pa Processing time: 30 to 600 seconds, preferably 60 to 300 seconds Raw material supply flow rate: 0.001 to 3 slm, preferably 0.01 to 2 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm is exemplified.

[0132] The process conditions for supplying reactants in step C2 within the overlap period T are: Treatment temperature: 300 to 800°C, preferably 400 to 650°C Treatment pressure: 1 to 4000 Pa, preferably 1 to 1333 Pa Processing time: 30 to 600 seconds, preferably 60 to 300 seconds Reactant supply flow rate: 0.01 to 30 slm, preferably 0.01 to 20 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm is exemplified.

[0133] After the overlap period T has ended, the processing conditions in steps C1 and C2 may be the same as the processing conditions in steps C1 and C2 in the above-described embodiment.

[0134] The processing conditions for supplying the raw material and catalyst in step C1 during the overlap period T are as follows: Treatment temperature: room temperature (25°C) to 200°C, preferably 25 to 150°C Processing pressure: 133~2666Pa Processing time: 30 to 600 seconds, preferably 60 to 300 seconds Raw material supply flow rate: 0.1~3slm Catalyst supply flow rate: 0.1~3slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm is exemplified.

[0135] During the overlap period T, the process conditions for supplying the reactants and catalyst in step C2 are as follows: Treatment temperature: room temperature (25°C) to 200°C, preferably 25 to 150°C Processing pressure: 133~2666Pa Processing time: 30 to 600 seconds, preferably 60 to 300 seconds Reactant supply flow rate: 0.1~3 slm Catalyst supply flow rate: 0.1~3slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm is exemplified.

[0136] After the overlap period T has ended, the processing conditions in steps C1 and C2 may be the same as the processing conditions in steps C1 and C2 in the above-described embodiment.

[0137] Other processing procedures and processing conditions can be the same as those in the above-described embodiments.

[0138] The embodiments shown in FIG. 5(b) and FIG. 5(c) also provide the same effects as those of the above-described embodiment.

[0139] Furthermore, according to these aspects, by providing an overlap period T in which steps B and C are performed in parallel, it is possible to shorten the total processing time for steps B and C and improve the productivity of the entire process.

[0140] It is preferable that the recipes used for each process are individually prepared according to the process content and recorded and stored in the storage device 121c via an electric communication line or an external storage device 123. Then, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the process content from the multiple recipes recorded and stored in the storage device 121c. This enables the processing device to perform various processes with good reproducibility on films of various film types, composition ratios, film qualities, and film thicknesses. It also reduces the burden on the operator, prevents operational errors, and enables each process to be started quickly.

[0141] The above-mentioned recipes do not necessarily have to be newly created, but may be prepared by modifying an existing recipe that has already been installed in the processing device. When modifying a recipe, the modified recipe may be installed in the processing device via an electric communication line or a recording medium on which the recipe has been recorded. Alternatively, an existing recipe that has already been installed in the processing device may be directly modified by operating the input / output device 122 provided in the existing processing device.

[0142] In the above-described embodiment, an example of processing using a batch processing apparatus that processes multiple substrates at a time has been described. The present disclosure is not limited to the above-described embodiment and can be applied, for example, to processing using a single-wafer processing apparatus that processes one or several substrates at a time. Furthermore, in the above-described embodiment, an example of processing using a processing apparatus having a hot-wall processing furnace has been described. The present disclosure is not limited to the above-described embodiment and can be applied to processing using a processing apparatus having a cold-wall processing furnace.

[0143] In the above-described embodiment, the processing sequence is performed in the same processing chamber of the same processing apparatus (in-situ). The present disclosure is not limited to the above-described embodiment, and for example, one step and another step of the processing sequence may be performed in different processing chambers of different processing apparatuses (ex-situ), or may be performed in different processing chambers of the same processing apparatus.

[0144] When using these processing devices, each process can be performed using the same processing procedures and conditions as in the above-described embodiments and modifications, and the same effects as in the above-described embodiments and modifications can be obtained.

[0145] The above-described embodiments and modifications may be used in combination as appropriate. The processing procedures and processing conditions in such a case may be the same as those of the above-described embodiments and modifications, for example. [Explanation of symbols]

[0146] 200 wafers (substrates)

Claims

1. (a) providing a substrate having a first surface and a second surface, with an inhibitor adsorbed on the first surface and the second surface; (b) exposing the substrate to a treatment agent to remove a portion of the inhibitor adsorbed on the first surface and a portion of the inhibitor adsorbed on the second surface, thereby reducing or neutralizing the film formation inhibitory effect of the inhibitor remaining on the second surface while maintaining the film formation inhibitory effect of the inhibitor remaining on the first surface; A processing method comprising:

2. 2. The treatment method according to claim 1, wherein the treatment agent used in (b) includes at least one of a nitrogen-containing substance, a hydrogen-containing substance, an oxygen-containing substance, a fluorine-containing substance, and a chlorine-containing substance.

3. 2. The processing method according to claim 1, wherein the processing agent used in (b) contains at least one of a nitrogen- and hydrogen-containing substance, a hydrogen- and oxygen-containing substance, a hydrogen- and fluorine-containing substance, a nitrogen- and fluorine-containing substance, a chlorine- and fluorine-containing substance, a fluorine-, nitrogen- and oxygen-containing substance, a hydrogen- and chlorine-containing substance, and a chlorine- and silicon-containing substance.

4. 2. The method of claim 1, wherein the treating agent used in (b) comprises hydrogen and an oxygen-containing substance.

5. The treating agent used in (b) is H ２ O or H ２ O ２ The method of claim 1 , comprising:

6. 2. The processing method according to claim 1, wherein the processing agent used in (b) contains pure water.

7. 10. The method of claim 1, wherein the first surface comprises an oxide and the second surface comprises a material different from the oxide.

8. The method of claim 1 , wherein the oxygen concentration of the first surface is higher than the oxygen concentration of the second surface.

9. 2. The method of claim 1, wherein the first surface comprises silicon and the second surface comprises silicon and / or a metal, or is silicon-free.

10. 2. The processing method according to claim 1, wherein in (a), the substrate is exposed to a modifying agent, thereby causing the inhibitor contained in the modifying agent to be adsorbed onto the first surface and the second surface.

11. the amount of the inhibitor adsorbed on the first surface is greater than the amount of the inhibitor adsorbed on the second surface; the density of the inhibitor adsorbed on the first surface is higher than the density of the inhibitor adsorbed on the second surface; a condition in which the coverage of the first surface by the inhibitor adsorbed to the first surface is higher than the coverage of the second surface by the inhibitor adsorbed to the second surface; The method according to claim 10, wherein (a) is carried out under at least one of the following conditions:

12. 11. The method of claim 10, wherein (a) is carried out under conditions such that the inhibitor adsorbed to the first surface forms a continuous layer and the inhibitor adsorbed to the second surface forms a discontinuous layer.

13. 2. The method according to claim 1, wherein in step (b), the amount of inhibitor adsorbed on the first surface that is removed is equal to or greater than the amount of inhibitor adsorbed on the second surface that is removed.

14. 2. The method according to claim 1, wherein in (b), the amount of inhibitor adsorbed on the first surface that is removed is greater than the amount of inhibitor adsorbed on the second surface that is removed.

15. The processing method according to any one of claims 1 to 14, further comprising the step of: (c) exposing the substrate after exposure to the processing agent to a film-forming agent, thereby forming a film on the second surface.

16. The processing method according to claim 15 , wherein the film-forming agent includes the processing agent, and (b) is performed so as to at least partially overlap with (c).

17. The processing method according to claim 15 , wherein the film-forming agent includes the processing agent, and (b) is performed at an early stage of (c).

18. (a) providing a substrate having a first surface and a second surface, with an inhibitor adsorbed on the first surface and the second surface; (b) exposing the substrate to a treatment agent to remove a portion of the inhibitor adsorbed on the first surface and a portion of the inhibitor adsorbed on the second surface, thereby reducing or neutralizing the film formation inhibitory effect of the inhibitor remaining on the second surface while maintaining the film formation inhibitory effect of the inhibitor remaining on the first surface; A method for manufacturing a semiconductor device having the above structure.

19. a device for preparing a substrate; a treatment agent exposure system for exposing the substrate to a treatment agent; (a) providing a substrate having a first surface and a second surface, the substrate having an inhibitor adsorbed on the first surface and the second surface; (b) exposing the substrate to the treatment agent to remove a portion of the inhibitor adsorbed on the first surface and a portion of the inhibitor adsorbed on the second surface, thereby reducing or neutralizing the film formation inhibitory effect of the inhibitor remaining on the second surface while maintaining the film formation inhibitory effect of the inhibitor remaining on the first surface; a control unit configured to be able to control the device and the treatment agent exposure system so as to perform the steps of: A processing device having:

20. (a) providing a substrate having a first surface and a second surface, with an inhibitor adsorbed on the first surface and the second surface; (b) exposing the substrate to a treatment agent to remove a portion of the inhibitor adsorbed on the first surface and a portion of the inhibitor adsorbed on the second surface, thereby reducing or neutralizing the film formation inhibitory effect of the inhibitor remaining on the second surface while maintaining the film formation inhibitory effect of the inhibitor remaining on the first surface; A program that causes a processing device to execute the above by a computer.

Images