Method of manufacturing semiconductor device, substrate processing method, substrate processing apparatus, and recording medium

Abstract

The present application relates to a method for manufacturing a semiconductor device, a substrate processing method, a substrate processing apparatus, and a recording medium. A technique for improving the embedding characteristics when filling a recess with a film is provided. The method includes: (a) a step of supplying a pretreatment gas to a substrate having a recess on its surface, thereby forming a base film in at least the upper part of the recess, the reactivity of which with a film formation inhibitor is higher than the reactivity of the film formation inhibitor with the surface in the recess; (b) a step of supplying a film formation inhibitor to the substrate, thereby forming a film formation inhibiting layer in a portion corresponding to the upper part of the recess on the surface of the base film formed in at least the upper part of the recess; and (c) a step of supplying a film formation gas to the substrate, thereby growing a film starting from a portion in the recess where the film formation inhibiting layer is not formed.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a semiconductor device, a substrate processing method, a substrate processing apparatus, and a recording medium. Background Art

[0002] With the miniaturization and complication of device shapes in recent LSI manufacturing processes, a technique (gap fill technique) for filling recesses such as trenches and holes formed on the surface of a substrate with a film is required. In the gap fill technique, there is a method of supplying an anti-film-forming gas to the upper part of a recess formed on the surface of a substrate, reducing the film-forming rate in the upper part of the recess, and forming a film in the recess (see, for example, Patent Document 1).

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2017-069407 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] However, in the case of using the above method, there are also cases where the anti-film-forming effect based on the anti-film-forming gas cannot be obtained sufficiently and sufficient embedding characteristics cannot be obtained.

[0008] An object of the present invention is to provide a technique for improving the embedding characteristics when filling a recess with a film.

[0009] Means for Solving the Problems

[0010] One aspect of the present invention provides a technique for performing the following steps:

[0011] (a) A step of forming a base film having a higher reactivity with an anti-film-forming agent than the reactivity of the anti-film-forming agent with the surface of the recess in at least the upper part of the recess by supplying a pre-treatment gas to a substrate having a recess on its surface;

[0012] (b) A step of forming an anti-film-forming layer on a part of the surface of the base film formed in at least the upper part of the recess corresponding to the upper part of the recess by supplying the anti-film-forming agent to the substrate; and

[0013] (c) A step of growing a film starting from a part of the recess where the anti-film-forming layer is not formed by supplying a film-forming gas to the substrate.

[0014] Advantages of the Invention

[0015] According to the present invention, a technique for improving the embedding characteristics when a film is filled into a concave portion can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a view showing a part of the processing furnace 202 in a longitudinal sectional view.

[0017] Figure 2 FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a view showing a part of the processing furnace 202 in a Figure 1 cross-sectional view taken along line A-A.

[0018] Figure 3 FIG. 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus preferably used in one embodiment of the present invention, and is a view showing a control system of the controller 121 in a block diagram.

[0019] Figure 4 FIGS. 4(a) to Figure 4 FIGS. 4(g) are partially enlarged cross-sectional views showing an example of a processing timing in the first embodiment of the present invention; Figure 4 FIG. 4(a) is a partially enlarged cross-sectional view of the surface of a wafer 200 provided with a concave portion 300; Figure 4 FIG. 4(b) is a partially enlarged cross-sectional view of the surface of the wafer 200 after a bottom film 304 is formed in the entire concave portion 300; Figure 4 FIG. 4(c) is a partially enlarged cross-sectional view of the surface of the wafer 200 after a film formation inhibiting layer 306 is formed on the upper part (the upper part of a part of the base film 304) in the concave portion 300; Figure 4 FIG. 4(d) is a partially enlarged cross-sectional view of the surface of the wafer 200 after a film 308 is formed in such a manner that the film grows starting from a non-formation portion of the film formation inhibiting layer 306 in the concave portion 300 to bury the lower part in the concave portion 300; Figure 4 FIG. 4(e) is a partially enlarged cross-sectional view of the surface of the wafer 200 after the film 308 is further grown starting from the state of FIG. 4(d) at the non-formation portion of the film formation inhibiting layer 306 to bury the lower part in the concave portion 300 compared with the central part; Figure 4 FIG. 4(f) is a partially enlarged cross-sectional view of the surface of the wafer 200 after the film 308 is further grown starting from the state of FIG. 4(e) at the non-formation portion of the film formation inhibiting layer 306 to bury the lower part in the concave portion 300 compared with the upper part; Figure 4 FIG. 4(g) is a partially enlarged cross-sectional view of the surface of the wafer 200 after the film 308 is formed starting from the state of FIG. 4(f) at the non-formation portion of the film formation inhibiting layer 306 to bury the lower part in the concave portion 300 compared with the upper part; Figure 4 FIG. 4(f) is a partially enlarged cross-sectional view of the surface of the wafer 200 after the film 308 is further grown starting from the state of FIG. 4(e) at the non-formation portion of the film formation inhibiting layer 306 to bury the lower part in the concave portion 300 compared with the upper part; Figure 4 FIG. 4(g) is a partially enlarged cross-sectional view of the surface of the wafer 200 after the film 308 is formed starting from the state of FIG. 4(f) at the non-formation portion of the film formation inhibiting layer 306 to bury the lower part in the concave portion 300 compared with the upper part; Figure 4The cross-sectional partial enlarged view of the surface of the wafer 200 after film growth starting from the non-formation portion of the film formation inhibiting layer 306 in the state of (f), forming the film 308 in the upper part within the concave portion 300 and other portions except within the concave portion 300, and then filling the entire concave portion 300 with the film 308.

[0020] Figure 5 of (a) to Figure 5 (i) is a cross-sectional partial enlarged view showing another example of the processing timing in the first embodiment of the present invention; Figure 5 of (a) to Figure 5 (c) are respectively Figure 4 of (a) to Figure 4 the same cross-sectional partial enlarged views as (c) of Figure 5 (d) is a cross-sectional partial enlarged view of the surface of the wafer 200 after film growth starting from the non-formation portion of the film formation inhibiting layer 306 within the concave portion 300 to form the film 308 in a manner of burying the lower part within the concave portion 300 and then removing the film formation inhibiting layer 306; Figure 5 (e) is a cross-sectional partial enlarged view of the surface of the wafer 200 after reforming the film formation inhibiting layer 306 in the upper part within the concave portion 300 where the film 308 is formed in a manner of burying the lower part; Figure 5 (f) is from Figure 5 the state of (e), further growing the film starting from the non-formation portion of the film formation inhibiting layer 306 to form the film 308 in a manner of burying the part below the central portion within the concave portion 300 and then removing the film formation inhibiting layer 306, which is a cross-sectional partial enlarged view of the surface of the wafer 200; Figure 5 (g) is a cross-sectional partial enlarged view of the surface of the wafer 200 after reforming the film formation inhibiting layer 306 in the upper part within the concave portion 300 where the film 308 is formed in a manner of burying the lower part compared to the central portion; Figure 5 (h) is from Figure 5 the state of (g), further growing the film starting from the non-formation portion of the film formation inhibiting layer 306 to form the film 308 in a manner of burying the lower part compared to the upper part within the concave portion 300 and then removing the film formation inhibiting layer 306, which is a cross-sectional partial enlarged view of the surface of the wafer 200; Figure 5 (i) is from Figure 5 the state of (h), further growing the film, forming the film 308 in the upper part within the concave portion 300 and other portions except within the concave portion 300, and then filling the entire concave portion 300 with the film 308, which is a cross-sectional partial enlarged view of the surface of the wafer 200.

[0021] Figure 6 of (a) to Figure 6 (a) to (g) are cross-sectional partial enlarged views showing an example of the processing timing in the second embodiment of the present invention.Figure 6 Fig. (a) is a partially enlarged sectional view of the surface of the wafer 200 provided with the recess 300; Figure 6 Fig. (b) is a partially enlarged sectional view of the surface of the wafer 200 after forming the base film 304 on the upper part within the recess 300; Figure 6 Fig. (c) is a partially enlarged sectional view of the surface of the wafer 200 after forming the film formation inhibiting layer 306 on the upper part within the recess 300 (the entire surface of the base film 304); Figure 6 Fig. (d) is a partially enlarged sectional view of the surface of the wafer 200 after growing a film starting from the non-formation part of the film formation inhibiting layer 306 within the recess 300 and burying the lower part within the recess 300 to form the film 308; Figure 6 Fig. (e) is from Figure 6 Fig. (d), a partially enlarged sectional view of the surface of the wafer 200 after further growing the film starting from the non-formation part of the film formation inhibiting layer 306 and burying the lower part within the recess 300 compared to the central part to form the film 308; Figure 6 Fig. (f) is from Figure 6 Fig. (e), a partially enlarged sectional view of the surface of the wafer 200 after further growing the film starting from the non-formation part of the film formation inhibiting layer 306 and burying the lower part within the recess 300 compared to the upper part to form the film 308; Figure 6 Fig. (g) is from Figure 6 Fig. (f), a partially enlarged sectional view of the surface of the wafer 200 after further growing the film starting from the non-formation part of the film formation inhibiting layer 306, forming the film 308 on the upper part within the recess 300 and other parts except within the recess 300, and filling the entire recess 300 with the film 308;

[0022] Figure 7 Figs. (a) to Figure 7 Fig. (i) is a partially enlarged sectional view showing another example of the processing timing in the second embodiment of the present invention; Figure 7 Figs. (a) to Figure 7 Figs. (c) are respectively the same as Figure 6 Figs. (a) to Figure 6 Figs. (c); Figure 7 Fig. (d) is a partially enlarged sectional view of the surface of the wafer 200 after growing a film starting from the non-formation part of the film formation inhibiting layer 306 within the recess 300, burying the lower part within the recess 300 to form the film 308, and removing the film formation inhibiting layer 306; Figure 7 Fig. (e) is a partially enlarged sectional view of the surface of the wafer 200 after reforming the film formation inhibiting layer 306 on the upper part within the recess 300 where the film 308 is formed by burying the lower part; Figure 7 Fig. (f) is fromFigure 7 A partial enlarged cross-sectional view of the surface of the wafer 200 after the film 308 is formed in such a manner that the film growth is further continued starting from the non-formation portion of the film formation inhibiting layer 306 so as to bury the lower portion compared to the central portion in the recess 300 and after the film formation inhibiting layer 306 is removed; Figure 7 A partial enlarged cross-sectional view of the surface of the wafer 200 after the film formation inhibiting layer 306 is reformed in the upper portion within the recess 300 in such a manner that the lower portion compared to the central portion is buried; Figure 7 The (h) of Figure 7 A partial enlarged cross-sectional view of the surface of the wafer 200 after the film growth is further continued starting from the non-formation portion of the film formation inhibiting layer 306 so as to bury the lower portion compared to the upper portion in the recess 300 and after the film formation inhibiting layer 306 is removed; Figure 7 The (i) of Figure 7 A partial enlarged cross-sectional view of the surface of the wafer 200 after the film is further grown from the state of (h), the film 308 is formed in the upper portion within the recess 300 and in other portions except within the recess 300, and the entire recess 300 is filled with the film 308.

[0023] Figure 8 It is a partial enlarged cross-sectional view showing an example in which the base film 304 is selectively formed in the upper portion within the recess 300.

[0024] Figure 9 The (a) of Figure 9 The (b) of Figure 9 A partial enlarged cross-sectional view showing an example in which the surface of the base film 304 in (a) is etched conformally and a part of the base film 304 remains in the upper portion within the recess 300. Detailed Description of the Invention

[0025] As a result of the in-depth study by the inventors of the present application, it has been found that when filling a recess provided on the surface of a substrate with a film, by previously forming a base film having certain specific properties against a film formation inhibitor in at least the upper portion within the recess, a film formation inhibiting layer can be appropriately and selectively formed in a portion corresponding to the upper portion within the recess. In addition, the inventors of the present application have found that thereby, the film can be appropriately grown upward from the bottom within the recess, and the filling characteristics can be improved. The present invention is proposed based on the above-mentioned insights found by the inventors of the present application. Hereinafter, two methods (the first embodiment and the second embodiment) in the present invention will be described.

[0026] <The First Embodiment in the Present Invention>

[0027] Hereinafter, mainly with reference to Figures 1 to 5 The first embodiment of the present invention will be described. It should be noted that the drawings used in the following description are all schematic, and the dimensional relationships, ratios of various elements shown in the drawings are not necessarily consistent with the actual ones. In addition, among multiple drawings, the dimensional relationships, ratios of various elements are not necessarily consistent either.

[0028] (1) Configuration of the substrate processing apparatus

[0029] As Figure 1 shown, the processing furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical in shape and is vertically installed by being supported on a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) a gas using heat.

[0030] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO 2 ) or silicon carbide (SiC), and is formed in a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS), and is formed in a cylindrical shape with open upper and lower ends. The upper end portion of the manifold 209 is configured to be engaged with the lower end portion of the reaction tube 203 and support the reaction tube 203. An O-ring 220a as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is vertically installed in the same manner as the heater 207. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the cylindrical hollow portion of the processing container. The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed inside the processing chamber 201.

[0031] Inside the processing chamber 201, nozzles 249a to 249c as the first to third supply portions are respectively provided so as to penetrate the side wall of the manifold 209. The nozzles 249a to 249c are also respectively referred to as the first to third nozzles. The nozzles 249a to 249c are made of a heat-resistant material such as quartz or SiC. Gas supply pipes 232a to 232c are respectively connected to the nozzles 249a to 249c. The nozzles 249a to 249c are different nozzles, and the nozzles 249a and 249c are respectively adjacently arranged to the nozzle 249b.

[0032] On the gas supply pipes 232a to 232c, mass flow controllers (MFCs) 241a to 241c as flow controllers (flow control units) and valves 243a to 243c as on-off valves are provided in sequence from the upstream side of the gas flow. On the downstream side of the gas supply pipe 232a compared with the valve 243a, gas supply pipes 232d and 232e are respectively connected. On the downstream side of the gas supply pipe 232b compared with the valve 243b, gas supply pipes 232f and 232h are respectively connected. On the downstream side of the gas supply pipe 232c compared with the valve 243c, a gas supply pipe 232g is connected. On the gas supply pipes 232d to 232h, MFCs 241d to 241h and valves 243d to 243h are provided in sequence from the upstream side of the gas flow. On the downstream side of the gas supply pipe 232c compared with the valve 243c, a remote plasma unit (hereinafter, RPU) 500 as a plasma excitation unit (plasma generation unit, plasma generator) for exciting the gas into a plasma state is provided. On the downstream side of the gas supply pipes 232b and 232h compared with the connection part, an RPU 502 is provided. The gas supply pipes 232a to 232h are made of a metal material such as SUS, for example.

[0033] As Figure 2 shown, the nozzles 249a to 249c are respectively arranged in a space in a circular ring shape when viewed from above between the inner wall of the reaction tube 203 and the wafer 200, and are erected from the lower part to the upper part of the inner wall of the reaction tube 203 in a direction upward of the arrangement direction facing the wafer 200. That is, the nozzles 249a to 249c are respectively arranged along the wafer arrangement area in an area on the side of the wafer arrangement area where the wafers 200 are arranged and horizontally surrounding the wafer arrangement area. When viewed from above, the nozzle 249b is arranged in a manner that it is aligned in a straight line with an exhaust port 231a to be described later with the center of the wafer 200 carried into the processing chamber 201 in between. The nozzles 249a and 249c are arranged along the inner wall of the reaction tube 203 (the outer peripheral part of the wafer 200) in a manner that they sandwich the straight line L passing through the centers of the nozzle 249b and the exhaust port 231a from both sides. The straight line L is also the straight line passing through the centers of the nozzle 249b and the wafer 200. That is, the nozzle 249c can also be arranged on the opposite side of the nozzle 249a with the straight line L in between. The nozzles 249a and 249c are symmetrically arranged with the straight line L as the symmetry axis. Gas supply holes 250a to 250c for supplying gas are respectively provided on the side surfaces of the nozzles 249a to 249c. The gas supply holes 250a to 250c are respectively opened in a manner that they face (are directly opposite to) the exhaust port 231a when viewed from above, and are configured to be able to supply gas toward the wafer 200. A plurality of the gas supply holes 250a to 250c are provided within the range from the lower part to the upper part of the reaction tube 203.

[0034] A source gas is supplied into the processing chamber 201 from the gas supply pipe 232a via the MFC 241a, the valve 243a, and the nozzle 249a.

[0035] A reaction gas is supplied into the processing chamber 201 from the gas supply pipe 232b via the MFC 241b, the valve 243b, and the nozzle 249b.

[0036] A fluorine-containing gas or a catalyst gas is supplied into the processing chamber 201 from the gas supply pipe 232c via the MFC 241c, the valve 243c, and the nozzle 249c.

[0037] An aminosilane gas is supplied into the processing chamber 201 from the gas supply pipe 232d via the MFC 241d, the valve 243d, the gas supply pipe 232a, and the nozzle 249a. Note that there are cases where the aminosilane gas contains a hydrocarbon group such as an alkyl group, and in such cases, the gas can also be referred to as a hydrocarbon group-containing gas.

[0038] An inert gas is supplied into the processing chamber 201 from the gas supply pipes 232e to 232g via the MFCs 241e to 241g, the valves 243e to 243g, the gas supply pipes 232a to 232c, and the nozzles 249a to 249c.

[0039] An oxidizing gas is supplied into the processing chamber 201 from the gas supply pipe 232h via the MFC 241h, the valve 243h, the gas supply pipe 232b, and the nozzle 249b.

[0040] The source gas supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a. The reaction gas supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b. The fluorine-containing gas supply system or the catalyst gas supply system is mainly composed of the gas supply pipe 232c, the MFC 241c, and the valve 243c. The aminosilane gas supply system (hydrocarbon group-containing gas supply system) is mainly composed of the gas supply pipe 232d, the MFC 241d, and the valve 243d. The aminosilane gas supply system can also be referred to as the Si-containing gas supply system. The inert gas supply system is mainly composed of the gas supply pipes 232e to 232g, the MFCs 241e to 241g, and the valves 243e to 243g. The oxidizing gas supply system is mainly composed of the gas supply pipe 232h, the MFC 241h, and the valve 243h.

[0041] Here, the source gas and the reaction gas function as film-forming gases. Therefore, one or both of the source gas supply system and the reaction gas supply system can also be referred to as the film-forming gas supply system. In addition, the source gas and the oxidation gas function as pretreatment gases. Therefore, the source gas supply system and the oxidation gas supply system can also be referred to as the pretreatment gas supply system. In addition, the fluorine-containing gas and the amino-silane-based gas (hydrocarbon group-containing gas) function as film-forming inhibitors. Therefore, the fluorine-containing gas supply system and the amino-silane-based gas supply system (hydrocarbon group-containing gas supply system) are also referred to as the film-forming inhibitor supply system. In addition, since the reaction gas or the oxidation gas also contains the gas that functions as an additive gas described later, one or both of the reaction gas supply system and the oxidation gas supply system can also be referred to as the additive gas supply system.

[0042] Any one or all of the above various supply systems can also be configured as an integrated supply system 248 integrated by valves 243a to 243h, MFCs 241a to 241h, etc. The integrated supply system 248 is respectively connected to the gas supply pipes 232a to 232h, and is configured to control the supply operations of various gases into the gas supply pipes 232a to 232h by the controller 121 described later, that is, the opening and closing operations of the valves 243a to 243h, the flow rate adjustment operations performed by the MFCs 241a to 241h, etc. The integrated supply system 248 is composed of an integrated unit of an integrated type or a split type, and is configured to be able to be disassembled and assembled with respect to the gas supply pipes 232a to 232h, etc. in units of integrated units, and to be able to perform maintenance, replacement, addition, etc. of the integrated supply system 248 in units of integrated units.

[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. As Figure 2As shown, the exhaust port 231a is disposed at a position that faces (is directly opposite to) the wafer 200 and the nozzles 249a to 249c (gas supply holes 250a to 250c) in a plan view. The exhaust port 231a may also be provided along the wafer arrangement area from the lower part to the upper part of 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 pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure regulation unit) are connected, and then a vacuum pump 246 as a vacuum exhaust device is connected. The APC valve 244 is configured to open and close the valve in a state where the vacuum pump 246 is operating, so that vacuum exhaust and stop of vacuum exhaust in the processing chamber 201 can be performed. In addition, in a state where the vacuum pump 246 is operating, the valve opening degree is adjusted based on the pressure information detected by the pressure sensor 245, so that the pressure in the processing chamber 201 can be adjusted. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. It is also possible to consider including the vacuum pump 246 in the exhaust system.

[0044] Below the manifold 209, a seal cover 219 as a furnace port cover body that can airtightly seal the lower end opening of the manifold 209 is provided. The seal cover 219 is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220b as a sealing member that abuts against the lower end of the manifold 209 is provided on the upper surface of the seal cover 219. Below the seal cover 219, a rotation mechanism 267 that rotates a susceptor 217 described later is provided. The rotation shaft 255 of the rotation mechanism 267 is connected to the susceptor 217 so as to penetrate the seal cover 219. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the susceptor 217. The seal cover 219 is configured to move up and down in the vertical direction by a susceptor elevator 115 as a lifting mechanism provided outside the reaction tube 203. The susceptor elevator 115 is a transfer device (transfer mechanism) configured to transfer (carry in and out) the wafer 200 into and out of the processing chamber 201 by lifting the seal cover 219.

[0045] Below the manifold 209, a gate plate 219s as a furnace port cover body is provided, and the gate plate 219s can airtightly seal the lower end opening of the manifold 209 in a state where the seal cover 219 is lowered and the susceptor 217 is carried out of the processing chamber 201. The gate plate 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c as a sealing member that abuts against the lower end of the manifold 209 is provided on the upper surface of the gate plate 219s. The opening and closing operation (lifting operation, rotation operation, etc.) of the gate plate 219s is controlled by a gate plate opening and closing mechanism 115s.

[0046] The susceptor 217 as a substrate support is configured to support multiple wafers 200, for example, 25 to 200 wafers, in a horizontal attitude with their centers aligned with each other and arranged in multiple stages in the vertical direction, that is, arranged at intervals. The susceptor 217 is made of a heat-resistant material such as quartz or SiC. A heat-insulating plate 218 made of a heat-resistant material such as quartz or SiC is supported in multiple stages at the lower part of the susceptor 217.

[0047] A temperature sensor 263 as a temperature detector is provided in the reaction tube 203. Based on the temperature information detected by the temperature sensor 263, the energization state of the heater 207 is adjusted so that the temperature in the processing chamber 201 becomes a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0048] As Figure 3 shown, the controller 121 as a control unit (control mechanism) is configured in the form of a computer having 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 perform data exchange with the CPU 121a via an internal bus 121e. An input / output device 122 configured in the form of a touch panel or the like is connected to the controller 121.

[0049] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. A control program for controlling the operation of the substrate processing apparatus, a process recipe including steps, conditions, etc. of the substrate processing described later, etc. are stored in the storage device 121c in a readable manner. The process recipe is a combination of the respective steps in the substrate processing described later in such a way that the controller 121 can execute it and obtain a prescribed result, and functions as a program. Hereinafter, the process recipe, the control program, etc. will also be simply referred to as a program. In addition, the process recipe will also be simply referred to as a recipe. In this specification, when using the term program, there are cases where it includes only the recipe, only the control program, or both the recipe and the control program. The RAM 121b is configured as a memory area (working area) that temporarily holds programs, data, etc. read by the CPU 121a.

[0050] 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, susceptor elevator 115, gate opening / closing mechanism 115s, etc.

[0051] The CPU 121a is configured to read a control program from the storage device 121c and execute it, and is capable of reading a process from the storage device 121c in response to an input of an operation command from the input / output device 122 or the like. The CPU 121a is configured to control various gas flow adjustment operations performed by the MFCs 241a to 241h, opening / closing operations of the valves 243a to 243h, opening / closing operations of the APC valve 244, pressure adjustment operations performed by the APC valve 244 based on the pressure sensor 245, start / stop of the vacuum pump 246, temperature adjustment operations of the heater 207 based on the temperature sensor 263, rotation and rotation speed adjustment operations of the susceptor 217 performed by the rotation mechanism 267, lifting operations of the susceptor 217 performed by the susceptor elevator 115, opening / closing operations of the gate 219s performed by the gate opening / closing mechanism 115s, etc., according to the content of the read process.

[0052] The controller 121 can be configured by installing the above program stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, magnetic disks such as HDDs, optical discs such as CDs, magneto-optical discs such as MOs, USB memories, semiconductor memories such as SSDs, etc. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, they will also be collectively referred to simply as recording media. In this specification, the case where the term recording medium is used may include only the storage device 121c, only the external storage device 123, or both the storage device 121c and the external storage device 123. It should be noted that the program can be provided to the computer without using the external storage device 123 by using a communication mechanism such as the Internet or a dedicated line.

[0053] (2) Substrate processing step

[0054] Mainly use Figure 4 of (a) to Figure 4 of (g) and Figure 5 of (a) to Figure 5 of (i) to illustrate an example of the following steps: Using the above substrate processing apparatus, as one step of the manufacturing process of semiconductor devices, a film is grown from the bottom up in recesses such as grooves and holes provided on the surface of the wafer 200 as a substrate. In the following description, the operations of each part constituting the substrate processing apparatus are controlled by the controller 121.

[0055] In Figure 4 from (a) to Figure 4 in (g) and Figure 5 from (a) to Figure 5 in the processing timing shown in (i), the following steps A, B, and C are performed, and after performing the following step A, the following steps B and C are performed a specified number of times (m times, where m is an integer of 1 or more):

[0056] Step A, in which a pretreatment gas is supplied to the wafer 200 having the recess 300 on its surface, so that a base film 304 having a higher reactivity with the film formation inhibitor than the reactivity of the film formation inhibitor with the surface in the recess 300 is formed at least in the upper part of the recess 300;

[0057] Step B, in which a film formation inhibitor is supplied to the wafer 200, so that a film formation inhibiting layer 306 is formed in a portion corresponding to the upper part in the recess 300 on the surface of the base film 304 formed at least in the upper part of the recess 300;

[0058] Step C, in which a film formation gas is supplied to the wafer 200, so that the film 308 grows starting from a portion where the film formation inhibiting layer 306 is not formed in the recess 300.

[0059] Step A is also referred to as base film formation. Step B is also referred to as film formation inhibiting layer formation. Step C is also referred to as selective growth (selective film formation) or bottom-up growth (bottom-up film formation).

[0060] In this specification, for convenience, there are also cases where the above processing timing is shown as follows. The same expression is also used in the description of the following other modes, modification examples, etc.

[0061] Step A → (Step B → Step C) × m

[0062] Here, the case of m = 1 corresponds to the processing timing shown in (a) to Figure 4 in Figure 4 (g), and the case of m > 1, that is, the case of m ≥ 2, corresponds to the processing timing shown in (a) to Figure 5 in Figure 5 in (i). In the processing timing shown in (a) to Figure 5 in Figure 5 in (i), the case of m = 3 is exemplified. The case of m = 1, that is, Figure 4 in (a) to Figure 4 in (g) can also be shown as follows.

[0063] Step A → Step B → Step C

[0064] It should be noted that Figure 4 from (a) to Figure 4of (g), Figure 5 of (a) - Figure 5 The processing timing shown in (i) of FIG. shows the following example: In step A, a base film 304 is formed throughout the recess 300, and in step B, a film formation inhibiting layer 306 is selectively formed on the upper part which is a part of the base film 304.

[0065] In this specification, when the term "wafer" is used, there are cases where it represents the wafer itself, and cases where it represents a laminate of a wafer and a specified layer or film formed on its surface. In this specification, when the term "surface of the wafer" is used, there are cases where it represents the surface of the wafer itself, and cases where it represents the surface of a specified layer formed on the wafer, etc. In this specification, when it is described that "a specified layer is formed on the wafer", there are cases where it represents directly forming a specified layer on the surface of the wafer itself, and cases where a specified layer is formed on a layer formed on the wafer, etc. In this specification, the cases of using the terms "substrate" and "recess" which is a part of the substrate have the same meaning as the case of using the term "wafer".

[0066] (Wafer Loading and Cassette Loading)

[0067] When a plurality of wafers 200 are loaded into the cassette 217 (wafer loading), the shutter 219s is moved by the shutter opening / closing mechanism 115s, and the lower end opening of the manifold 209 is opened (shutter opening). After that, as Figure 1 shown, the cassette 217 supporting a plurality of wafers 200 is lifted by the cassette elevator 115 and carried into the processing chamber 201 (cassette loading). In this state, the seal cover 219 makes the lower end of the manifold 209 in a sealed state by means of the O-ring 220b.

[0068] Here, as the wafers 200 loaded into the cassette 217, single crystal silicon (Si) wafers can be used. In addition, as described above, as Figure 4 in (a) of Figure 5 as shown in (a) of FIG., recesses 300 are provided on the surface of the wafers 200 loaded into the cassette 217. There is no particular limitation on the material of the surface (the outermost surface) inside the recess 300, that is, the surface of the inner wall of the recess 300. For example, single crystal Si (the single crystal Si wafer itself), silicon film (Si film), germanium film (Ge film), silicon germanium film (SiGe film), silicon carbide film (SiC film), silicon nitride film (SiN film), silicon carbonitride film (SiCN film), silicon oxide film (SiO film), silicon oxynitride (SiON), silicon oxycarbide film (SiOC film), silicon oxynitride film (SiOCN film), silicon boron nitride film (SiBN film), silicon boron carbonitride film (SiBCN film), boron nitride film (BN film), etc. can be cited. For example, there are cases where it is at least any one of them.

[0069] (Pressure regulation and temperature regulation)

[0070] Vacuum exhaust (pressure reduction exhaust) is performed by a vacuum pump 246 so that the pressure (vacuum degree) in the processing chamber 201, that is, the space where the wafer 200 is located, reaches a desired pressure. At this time, the pressure in the processing chamber 201 is measured by a pressure sensor 245, and feedback control is performed on the APC valve 244 based on the measured pressure information. In addition, heating is performed by a heater 207 so that the wafer 200 in the processing chamber 201 reaches a desired processing temperature. At this time, feedback control is performed on the energization state of the heater 207 based on the temperature information detected by a temperature sensor 263 so that a desired temperature distribution is achieved in the processing chamber 201. In addition, rotation of the wafer 200 by a rotation mechanism 267 is started. Exhaust in the processing chamber 201, heating of the wafer 200, and rotation are all continuously performed at least until the processing of the wafer 200 ends.

[0071] After that, step A, step B, and step C are sequentially executed. Hereinafter, each of the above steps will be described.

[0072] 〔Step A (formation of base film)〕

[0073] In this step, by supplying a pretreatment gas to the wafer 200, a base film 304 having a higher reactivity with the film formation inhibitor than the reactivity of the film formation inhibitor with the surface in the concave portion 300 is formed at least in the upper part of the concave portion 300. Here, as shown in (b) of Figure 4 (b) of Figure 5 (b) of

[0074] for example, in this step, by alternately supplying a source gas and a modifying gas to the wafer 200 as the pretreatment gas, the base film 304 can be deposited throughout the concave portion 300 (Method 1-A1). Or, by supplying a modifying gas to the wafer 200 as the pretreatment gas, the surface in the concave portion 300 can be modified to form the base film 304 throughout the concave portion 300 (Method 1-A2). By either method, a conformal base film 304 can be formed throughout the concave portion 300.

[0075] As the base film 304, for example, an oxygen-containing (O) film such as a SiO film, a SiON film, a SiOC film, or a SiOCN film, that is, a film capable of forming an oxide film system, can be used. As the base film 304, among the O-containing films, a film containing Si and O is preferred, and a SiO film is more preferred. Hereinafter, an example of forming a SiO film as the base film 304 will be described. It should be noted that as the base film 304, a film having the same material as the surface in the concave portion 300 can also be used, and a film having a different material from the surface in the concave portion 300 is preferably used.

[0076] For example, in the case of forming an SiO film as the base film 304, an oxidation gas can be used as the modifying gas. That is, in this case, as the pretreatment gas, a source gas and an oxidation gas (modifying gas) are alternately supplied to the wafer 200, so that an SiO film can be deposited in the recess 300 as the base film 304 (Method 1-A1).

[0077] In addition, for example, by supplying an oxidation gas (modifying gas) to the wafer 200 as the pretreatment gas, the surface in the recess 300 can be oxidized (modified), and an SiO film can be formed in the recess 300 as the base film 304 (Method 1-A2).

[0078] As shown in Method 1-A1, when a source gas and an oxidation gas are alternately supplied to the wafer 200 as the pretreatment gas, it is preferable to sandwich a purge of the inside of the processing chamber 201 with an inert gas therebetween. That is, in this step, it is preferable to perform a cycle that is not performed simultaneously in the following steps a prescribed number of times (d times, d is an integer of 1 or more): a step of supplying a source gas to the wafer 200; a step of purging the inside of the processing chamber 201; a step of supplying an oxidation gas; and a step of purging the inside of the processing chamber 201. In addition, a catalyst gas can also be supplied together with at least any one of the source gas and the oxidation gas. In this case, the processing temperature can be lowered, and film formation can be performed at room temperature. The processing timing of Method 1-A1 can be expressed as follows, and any one of the following four processing timings can be performed.

[0079] (Source gas → Purge → Oxidation gas → Purge) × d

[0080] (Source gas + Catalyst gas → Purge → Oxidation gas → Purge) × d

[0081] (Source gas → Purge → Oxidation gas + Catalyst gas → Purge) × d

[0082] (Source gas + Catalyst gas → Purge → Oxidation gas + Catalyst gas → Purge) × d

[0083] When an oxidation gas is used as the pretreatment gas, the valve 243h is opened, and the oxidation gas is supplied into the gas supply pipe 232h. The flow rate of the oxidation gas is adjusted by the MFC241h, supplied into the processing chamber 201 via the nozzle 249b, and exhausted from the exhaust port 231a. At this time, the oxidation gas is supplied to the wafer 200. At this time, the valves 243e to 243g can also be opened, and inert gases can be supplied into the processing chamber 201 via the nozzles 249a to 249c, respectively.

[0084] When further using the source gas as the pretreatment gas, open valve 243a to supply the source gas into gas supply pipe 232a. The source gas is flow-regulated by MFC241a, supplied into processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, the source gas is supplied to wafer 200. At this time, valves 243e - 243g can also be opened to supply inert gases into processing chamber 201 via nozzles 249a - 249c respectively.

[0085] When further using the catalyst gas as the pretreatment gas, open valve 243c to supply the catalyst gas into gas supply pipe 232c. The catalyst gas is flow-regulated by MFC241c, supplied into processing chamber 201 via nozzle 249c, and exhausted from exhaust port 231a. At this time, the catalyst gas is supplied to wafer 200. At this time, valves 243e - 243g can also be opened to supply inert gases into processing chamber 201 via nozzles 249a - 249c respectively.

[0086] When alternately supplying the source gas and the oxidation gas and purging the inside of processing chamber 201 with an inert gas between them, open valves 243e - 243g to supply inert gases into gas supply pipes 232e - 232g respectively. The inert gases are flow-regulated by MFC241e - 241g, supplied into processing chamber 201 via nozzles 249a - 249c, and exhausted from exhaust port 231a. At this time, the inside of processing chamber 201 is purged with the inert gas.

[0087] In this step, according to Method 1 - A1, the processing conditions when supplying the source gas in the case of forming a SiO film as the base film 304 can be exemplified as follows:

[0088] Processing temperature: room temperature (25°C) to 700°C, preferably 200 - 650°C

[0089] Processing pressure: 1 - 2000 Pa, preferably 5 - 1000 Pa

[0090] Source gas supply flow rate: 1 - 3000 sccm, preferably 1 - 500 sccm

[0091] Source gas supply time: 1 - 120 seconds, preferably 1 - 60 seconds

[0092] Catalyst gas supply flow rate: 0 - 2000 sccm

[0093] Inert gas supply flow rate (for each gas supply pipe): 0 - 20000 sccm.

[0094] In this step, according to Method 1-A1, the processing conditions for supplying the oxidation gas when forming the SiO film on the base film 304 are exemplified as follows:

[0095] Processing temperature: room temperature (25°C) to 700°C, preferably 200 to 650°C

[0096] Processing pressure: 1 to 4000 Pa, preferably 1 to 3000 Pa

[0097] Oxidation gas supply flow rate: 1 to 10000 sccm, preferably 100 to 2000 sccm

[0098] Oxidation gas supply time: 10 to 120 seconds, preferably 15 to 60 seconds

[0099] Catalyst gas supply flow rate: 0 to 2000 sccm

[0100] Inert gas supply flow rate (for each gas supply pipe): 0 to 20000 sccm.

[0101] In this step, according to Method 1-A1, the processing conditions for purging the inside of the processing chamber 201 when forming the SiO film on the base film 304 are exemplified as follows:

[0102] Processing temperature: room temperature (25°C) to 700°C, preferably 200 to 650°C

[0103] Processing pressure: 1 to 100 Pa, preferably 1 to 20 Pa

[0104] Inert gas supply flow rate (for each gas supply pipe): 500 to 20000 sccm

[0105] Inert gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds.

[0106] In this step, according to Method 1-A2, the processing conditions for supplying the oxidation gas when forming the SiO film on the base film 304 are exemplified as follows:

[0107] Processing temperature: 350 to 1200°C, preferably 400 to 800°C

[0108] Processing pressure: 1 to 4000 Pa, preferably 1 to 3000 Pa

[0109] Oxidation gas supply flow rate: 1 to 10000 sccm, preferably 100 to 2000 sccm

[0110] Oxidation gas supply time: 1 to 120 minutes, preferably 3 to 60 minutes

[0111] Inert gas supply flow rate (for each gas supply pipe): 0 to 20,000 sccm.

[0112] It should be noted that the expression of a numerical range such as "350 to 1200 °C" in this specification means that the lower limit value and the upper limit value are included in the range. Thus, for example, "350 to 1200 °C" means "350 °C or higher and 1200 °C or lower". The same applies to other numerical ranges. It should be noted that the processing temperature represents the temperature of the wafer 200, and the processing pressure represents the pressure inside the processing chamber 201. In addition, a gas supply flow rate of 0 sccm means that the gas is not supplied. This is the same in the following descriptions.

[0113] As a source gas, for example, monochlorosilane (SiH 3 Cl, abbreviation: MCS) gas, dichlorosilane (SiH 2 Cl 2 , abbreviation: DCS) gas, trichlorosilane (SiHCl 3 , abbreviation: TCS) gas, tetrachlorosilane (SiCl 4 , abbreviation: STC) gas, hexachloroethylsilane gas (Si 2 Cl 6 , abbreviation: HCDS) gas, octachlorotrisilane (Si 3 Cl 8 , abbreviation: OCTS) gas and other chlorosilane gases can be used. In addition, as a source gas, for example, silicon tetrafluoride (SiF 4 ) gas, difluorosilane (SiH 2 F 2 ) gas and other fluorosilane gases, silicon tetrabromide (SiBr 4 ) gas, dibromosilane (SiH 2 Br 2 ) gas and other bromosilane gases, silicon tetraiodide (SiI 4 ) gas, diiodosilane (SiH 2 I 2 ) gas and other iodosilane gases can be used. In addition, as a source gas, for example, tetra(dimethylamino)silane (Si[N(CH 3 ) 2 4 , abbreviation: 4DMAS) gas, tris(dimethylamino)silane (Si[N(CH 3 ) 2 3 H, abbreviation: 3DMAS) gas, bis(diethylamino)silane (Si[N(C 2 H 5 ) 2 2 H​​​2 , abbreviation: BDEAS) gas, bis(tert-butylamino)silane (SiH 2 [NH(C 4 H 9 )]2, abbreviation: BTBAS) gas, (diisopropylamino)silane (SiH 3 [N(C 3 H 7 ) 2 , abbreviation: DIPAS) gas, (ethylmethylamino)silane (SiH 3 [N(CH 3 )(C 2 H 5 )]) gas, (dimethylamino)silane (SiH 3 [N(CH 3 ) 2 ) gas, (di-sec-butylamino)silane (SiH 3 [H(C 4 H 9 ) 2 ) gas, (dimethylpiperidyl)silane (SiH 3 [NC 5 H 8 (CH 3 ) 2 ) gas, (diethylpiperidyl)silane (SiH 3 [NC 5 H 8 (C 2 H 5 ) 2 ) gas and other aminosilane gases. As the source gas, one or more of the above can be used.

[0114] As the oxidation gas, for example, oxygen (O 2 ) gas, nitrous oxide (N 2 O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO 2 ) gas, ozone (O 3 ) gas, water vapor (H 2 O gas), carbon monoxide (CO) gas, carbon dioxide (CO 2 ) gas, O 2 gas + hydrogen (H 2 ) gas, O 3 gas + H 2 gas, H 2 O gas + H 2 gas, etc. As the oxidation gas, one or more of them can be used.

[0115] It should be noted that in this specification, "O3 Gas + H 2 The combined description of two gases such as "gas" represents O 3 Gas and H 2 A mixed gas of gas. When supplying the mixed gas, it is also possible to mix the two gases in the supply pipe (pre-mixing) and then supply them into the processing chamber 201, or supply the two gases into the processing chamber 201 from different supply pipes respectively and mix them in the processing chamber 201 (post-mixing).

[0116] As the inert gas, for example, nitrogen (N 2 ) gas can be used. In addition, noble gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas can be used. As the inert gas, one or more of them can be used. This is the same in each of the steps described later.

[0117] Based on the above methods, by performing this step under the above processing conditions using the above gases, as shown in Figure 4 (b) of Figure 5 (b) of

[0118] It should be noted that in step B described later, when a fluorine (F) capping layer or a hydrocarbon group capping layer is formed as the film formation inhibiting layer 306 and a film of a material other than the SiO film is exposed on the surface in the concave portion 300, if the film formation inhibiting layer 306 is directly formed on the surface in the concave portion 300 without forming the base film 304, the film formation inhibiting effect generated by the F capping layer and the hydrocarbon group capping layer formed in the concave portion 300 may be reduced. That is, there may be a situation where the film formation inhibiting effect generated by the F capping layer and the hydrocarbon group capping layer is insufficient or limited.

[0119] One of the reasons is considered to be: when the surface in the concave portion 300 contains elements other than Si and O, such as elements such as N and C, for example, the density of the F capping layer and the hydrocarbon group capping layer is reduced due to the elements other than Si and O on the surface in the concave portion 300. In addition, another reason is considered to be: for example, due to the elements other than Si and O on the surface in the concave portion 300, when forming the F capping layer and the hydrocarbon group capping layer, the energy for the film formation inhibitor to adsorb to the base film 304 becomes weak, and the film formation inhibitor adsorbed to the base film 304, that is, F capping and hydrocarbon group capping, becomes easy to detach.

[0120] In contrast, according to the present embodiment, even when the surface in the recess 300 contains elements other than Si and O, such as N, C, etc., for example, a SiO film is formed as the base film 304 on the entire surface in the recess 300, and an F capping layer and a hydrocarbon group capping layer are formed as the film formation inhibiting layer 306 on the SiO film. Thereby, it is possible to avoid being affected by elements other than Si and O in the surface in the recess 300 when forming the F capping layer and the hydrocarbon group capping layer, and it is possible to improve the film formation inhibiting effect based on the F capping layer and the hydrocarbon group capping layer.

[0121] According to the above, when forming the F capping layer and the hydrocarbon group capping layer as the film formation inhibiting layer 306 in step B, it is preferable to use an O-containing film as the base film 304, more preferably an Si- and O-containing film among the O-containing films, and still more preferably a SiO film among the Si- and O-containing films.

[0122] When the base film 304 does not contain elements other than Si and O, it is possible to suppress a decrease in the density of the F capping layer and the hydrocarbon group capping layer formed as the film formation inhibiting layer 306 on the base film 304. In addition, when forming the F capping layer and the hydrocarbon group capping layer, it is possible to sufficiently increase the energy of the base film 304 to adsorb the film formation inhibitor, and it is possible to suppress the detachment of the film formation inhibitor adsorbed on the base film 304, that is, the detachment of F capping and hydrocarbon group capping.

[0123] In addition, when forming the F capping layer as the film formation inhibiting layer 306, F-containing radicals are generated, but it is also possible to suppress etching damage to the base film 304 and the inner surface of the recess 300 caused by the F-containing radicals through the strong Si-O bonds contained in the base film 304. This effect can be obtained when the base film 304 contains Si-O bonds, and furthermore, it will be more significantly generated when the base film 304 does not contain elements other than Si and O.

[0124] (Purge)

[0125] After forming the base film 304 in the recess 300, an inert gas is supplied into the processing chamber 201 from the nozzles 249a to 249c, and exhausted from the exhaust port 231a. The inert gas supplied from the nozzles 249a to 249c functions as a purge gas, whereby the inside of the processing chamber 201 is purged, and gases, reaction by-products, etc. remaining in the processing chamber 201 are removed from the processing chamber 201.

[0126] [Step B (Film Formation Inhibiting Layer Formation)]

[0127] After step A is completed and the inside of the processing chamber 201 is purged, step B is performed. By supplying a film formation inhibitor to the wafer 200 in step B, as in Figure 4 (c) of Figure 5As shown in (c) of , a film formation inhibiting layer 306 is formed in a portion of the surface of the base film 304 formed throughout the recess 300 corresponding to the upper portion within the recess 300. In this step, it is preferable to selectively (preferably) form the film formation inhibiting layer 306 in a portion of the surface of the base film 304 formed within the recess 300 corresponding to the upper portion within the recess 300.

[0128] For example, in this step, the film formation inhibitor can be supplied under conditions where the film formation inhibitor is consumed and / or inactivated in the upper portion within the recess 300. Here, the conditions where the film formation inhibitor is consumed and / or inactivated in the upper portion within the recess 300 refer to the conditions where the film formation inhibitor is consumed in the upper portion within the recess 300, the conditions where the film formation inhibitor is inactivated in the upper portion within the recess 300, or the conditions where the film formation inhibitor is consumed and inactivated in the upper portion within the recess 300. By supplying the film formation inhibitor under such conditions, the film formation inhibitor will be consumed in the upper portion within the recess 300 and not reach the lower portion within the recess 300, or the film formation inhibitor will be inactivated in the upper portion within the recess 300 and not reach the lower portion within the recess 300 in an active state, or both of the above situations will occur.

[0129] Under such conditions, by supplying a fluorine (F)-containing gas as the film formation inhibitor, an F-capping layer can be selectively formed as the film formation inhibiting layer 306 in a portion of the surface of the base film 304 formed within the recess 300 corresponding to the upper portion within the recess 300.

[0130] For example, by supplying a fluorine (F)-containing gas as the film formation inhibitor under conditions where the fluorine (F)-containing gas thermally decomposes, the fluorine (F)-containing radicals generated by the thermal decomposition of the film formation inhibitor, i.e., the fluorine (F)-containing gas, can be consumed and / or inactivated in the upper portion within the recess 300. Thereby, an F-capping layer can be selectively formed as the film formation inhibiting layer 306 in a portion of the surface of the base film 304 formed within the recess 300 corresponding to the upper portion within the recess 300 by the action of the fluorine (F)-containing radicals (Method 1-B1).

[0131] In addition, for example, by plasma-exciting and supplying a fluorine (F)-containing gas as the film formation inhibitor, the fluorine (F)-containing radicals generated by plasma-exciting the film formation inhibitor, i.e., the fluorine (F)-containing gas, can be consumed and / or inactivated in the upper portion within the recess 300. Thereby, an F-capping layer can be selectively formed as the film formation inhibiting layer 306 in a portion of the surface of the base film 304 formed within the recess 300 corresponding to the upper portion within the recess 300 by the action of the fluorine (F)-containing radicals (Method 1-B2).

[0132] In addition, for example, by supplying a fluorine-containing gas and an additive gas that reacts with the fluorine-containing gas as a film formation inhibitor, fluorine-containing radicals generated by the film formation inhibitor, i.e., the fluorine-containing gas and the reaction of the fluorine-containing gas with the additive gas, can be consumed and / or deactivated in the upper part of the recess 300. Thereby, by the action of the fluorine-containing radicals, an F-capping layer can be selectively formed on the part of the surface of the base film 304 formed in the recess 300 corresponding to the upper part of the recess 300 as the film formation inhibiting layer 306 (Method 1-B3).

[0133] In addition, by supplying a hydrocarbon group-containing gas as a film formation inhibitor under such conditions, a hydrocarbon group-capping layer can be selectively formed as the film formation inhibiting layer 306 on the part of the surface of the base film 304 formed in the recess 300 corresponding to the upper part of the recess 300.

[0134] For example, by supplying a hydrocarbon group-containing gas as a film formation inhibitor under conditions where it is difficult to reach the bottom of the recess 300, i.e., gas-deficient conditions, the film formation inhibitor can be consumed and / or deactivated in the upper part of the recess 300. Thereby, the part of the surface of the base film 304 formed in the recess 300 corresponding to the upper part of the recess 300 can be selectively chemisorbed with the hydrocarbon group-containing gas to form a hydrocarbon group-capping layer as the film formation inhibiting layer 306 (Method 1-B4).

[0135] When using a fluorine-containing gas as a film formation inhibitor, the valve 243c is opened to supply the fluorine-containing gas into the gas supply pipe 232c. The flow rate of the fluorine-containing gas is adjusted by the MFC241c, supplied into the processing chamber 201 via the nozzle 249c, and exhausted from the exhaust port 231a. At this time, the fluorine-containing gas is supplied to the wafer 200. At this time, the valves 243e to 243g can also be opened to supply inert gases into the processing chamber 201 via the nozzles 249a to 249c respectively. It should be noted that when supplying the fluorine-containing gas into the processing chamber 201 via the gas supply pipe 232c, the fluorine-containing gas can be plasma-excited and supplied by applying high-frequency power (RF power) to the RPU500.

[0136] When using an additive gas together with the fluorine-containing gas as a film formation inhibitor, the valve 243b or the valve 243h is opened to supply the additive gas into the gas supply pipe 232b or the gas supply pipe 232h. The flow rate of the additive gas is adjusted by the MFC241b or the MFC241h, supplied into the processing chamber 201 via the nozzle 249b, and exhausted from the exhaust port 231a. At this time, the additive gas is supplied to the wafer 200. At this time, the valves 243e to 243g can also be opened to supply inert gases into the processing chamber 201 via the nozzles 249a to 249c respectively.

[0137] When using a hydrocarbon group-containing gas as a film formation inhibitor, valve 243d is opened, and the hydrocarbon group-containing gas is supplied into gas supply pipe 232d. The flow rate of the hydrocarbon group-containing gas is adjusted by MFC241d, supplied into processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, the hydrocarbon group-containing gas is supplied to wafer 200. At this time, valves 243e to 243g can also be opened, and an inert gas is supplied into processing chamber 201 via nozzles 249a to 249c, respectively.

[0138] In this step, according to Method 1-B1, the processing conditions when supplying the F-containing gas are exemplified as follows:

[0139] Processing temperature: 200 to 600 °C, preferably 350 to 500 °C

[0140] Processing pressure: 1 to 2000 Pa, preferably 1 to 1000 Pa

[0141] F-containing gas supply flow rate: 1 to 100 sccm, preferably 10 to 100 sccm

[0142] F-containing gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds

[0143] Inert gas supply flow rate (for each gas supply pipe): 0 to 20000 sccm.

[0144] In this step, according to Method 1-B2, the processing conditions when supplying the F-containing gas are exemplified as follows:

[0145] Processing temperature: room temperature (25 °C) to 600 °C, preferably 100 to 300 °C

[0146] Processing pressure: 1 to 2000 Pa, preferably 1 to 1000 Pa

[0147] F-containing gas supply flow rate: 1 to 3000 sccm, preferably 1 to 500 sccm

[0148] F-containing gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds

[0149] Inert gas supply flow rate (for each gas supply pipe): 0 to 20000 sccm

[0150] High-frequency power (RF power): 25 to 1500 W.

[0151] In this step, according to Method 1-B3, the processing conditions when supplying the F-containing gas + additive gas are exemplified as follows:

[0152] Processing temperature: room temperature (25 °C) to 600 °C, preferably room temperature to 300 °C

[0153] Processing pressure: 1 - 2000 Pa, preferably 1 - 1000 Pa

[0154] Supply flow rate of F - containing gas: 1 - 3000 sccm, preferably 1 - 500 sccm

[0155] Supply flow rate of additive gas: 1 - 3000 sccm, preferably 1 - 500 sccm

[0156] Supply time of F - containing gas + additive gas: 1 - 120 seconds, preferably 1 - 60 seconds

[0157] Supply flow rate of inert gas (for each gas supply pipe): 0 - 20000 sccm.

[0158] In this step, according to Method 1 - B4, as the processing conditions when supplying a hydrocarbon - containing gas, the following can be exemplified:

[0159] Processing temperature: room temperature (25°C) - 600°C, preferably 100 - 500°C

[0160] Processing pressure: 1 - 2000 Pa, preferably 1 - 1000 Pa

[0161] Supply flow rate of hydrocarbon - containing gas: 1 - 100 sccm, preferably 10 - 100 sccm. Supply time of hydrocarbon - containing gas: 1 - 120 seconds, preferably 1 - 60 seconds

[0162] Supply flow rate of inert gas (for each gas supply pipe): 0 - 20000 sccm.

[0163] As the F - containing gas, for example, nitrogen trifluoride (NF 3 ) gas, chlorine fluoride (ClF) gas, chlorine trifluoride (ClF 3 ) gas, fluorine (F 2 ) gas, nitrosyl fluoride (FNO) gas, tetrafluoromethane (CF 4 ) gas, hexafluoroethane (C 2 F 6 ) gas, octafluoropropane (C 3 F 8 ) gas, etc. As the F - containing gas, one or more of them can be used.

[0164] As the additive gas, for example, ammonia (NH 3 ) gas, hydrogen (H 2 ) gas, oxygen (O 2 ) gas, nitrous oxide (N 2 O) gas, nitric oxide (NO) gas, isopropyl alcohol ((CH 3 ) 2CHOH, abbreviation: IPA) gas, methanol (CH 3 OH) gas, water vapor (H 2 O gas), etc. As the additive gas, one or more of them can be used.

[0165] As the hydrocarbon group-containing gas, for example, a gas containing an alkyl group can be used. As the gas containing an alkyl group, for example, a gas containing an alkylsilyl group in which an alkyl group is coordinated to Si, that is, an alkylsilane gas, can be used. An alkyl group is a general term for the remaining atomic group after removing one hydrogen (H) atom from an alkane (a chain saturated hydrocarbon represented by the general formula C n H 2n+2 ), and is a functional group represented by the general formula C n H 2n+1 . As the alkyl group, an alkyl group having 1 to 5 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. The alkyl group can be either linear or branched. As the alkyl group, for example, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, etc. can be cited. Since the alkyl group is bonded to Si which is the central atom of the alkylsilane molecule, the alkyl group in the alkylsilane can also be called a ligand (coordination body) or an alkyl ligand.

[0166] The hydrocarbon group-containing gas may further contain an amino group. That is, the hydrocarbon group-containing gas may contain a hydrocarbon group and an amino group. As the gas containing a hydrocarbon group and an amino group, for example, an alkylaminosilane gas containing an alkyl group directly bonded to Si as the central atom and an amino group directly bonded to Si as the central atom can be used. An amino group is a functional group in which one or two hydrocarbon groups are coordinated to one nitrogen (N) atom (a functional group in which one or both of the hydrogen (H) atoms of the amino group represented by -NH 2 are replaced by a hydrocarbon group). When two hydrocarbon groups that form part of the amino group are coordinated to one N, the two hydrocarbon groups can be either the same hydrocarbon group or different hydrocarbon groups. The hydrocarbon group that forms part of the amino group is the same as the above-mentioned hydrocarbon group. In addition, the amino group may have a cyclic structure. The amino group directly bonded to Si as the central atom in the alkylaminosilane can also be called a ligand or an amino ligand. In addition, the alkyl group directly bonded to Si as the central atom in the alkylaminosilane can also be called a ligand or an alkyl ligand.

[0167] As the alkylaminosilane gas, for example, a gas of an aminosilane compound represented by the following formula [1] can be used.

[0168] SiA x [(NB 2 ) (4-x) [1]

[0169] In formula [1], A represents a hydrogen (H) atom, an alkyl group or an alkoxy group, B represents an H atom or an alkyl group, and x represents an integer from 1 to 3. It should be noted that when x is 1, A represents an alkyl group, and when x is 2 or 3, at least one of the As represents an alkyl group.

[0170] In formula [1], the alkyl group represented by A is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group represented by A can be either linear or branched. Examples of the alkyl group represented by A include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. The alkoxy group represented by A is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms. The alkyl group in the alkoxy group represented by A is the same as the alkyl group represented by A above. When x is 2 or 3, the two or three As can be the same or different. The alkyl group represented by B is the same as the alkyl group represented by A above. In addition, the two Bs can be the same or different, and when x is 1 or 2, the multiple (NB 2 ) can be the same or different. Furthermore, two Bs can be bonded to form a ring structure, and the formed ring structure can also have substituents such as an alkyl group.

[0171] As the alkylaminosilane gas, for example, a gas of a compound containing one amino group and three alkyl groups in one molecule can be used. That is, a gas of a compound in which A in formula [1] is an alkyl group and x is 3 can be used. As the alkylaminosilane gas, (alkylamino)alkylsilane gas can be used. Specifically, for example, (dimethylamino)trimethylsilane ((CH 3 ) 2 NSi(CH 3 ) 3 , abbreviation: DMATMS) gas, (diethylamino)trimethylsilane ((C 2 H 5 ) 2 NSi(CH 3 ) 3 , abbreviation: DEATMS) gas, (diethylamino)triethylsilane ((C 2 H 5 ) 2 NSi(C 2 H 5 ) 3 , abbreviation: DEATES) gas, (dimethylamino)triethylsilane ((CH 3 ) 2 NSi(C 2 H 5 ) 3, Abbreviation: (Dialkylamino)trialkylsilane gases such as DMATES). It should be noted that on the Si serving as the central atom in DMATMS, DEATMS, DEATES, DMATES, etc., in addition to being bonded to one amino group (dimethylamino, diethylamino), three alkyl groups (methyl, ethyl) are also bonded. That is, DMATMS, DEATMS, DEATES, DMATES, etc. contain one amino ligand and three alkyl ligands.

[0172] According to each of the above methods, by using each of the above gases under each of the above treatment conditions in this step, thus as Figure 4 in (c) of Figure 5 shown in (c) of

[0173] (Purge)

[0174] After forming the film formation inhibiting layer 306 on the surface of the base film 304 corresponding to the upper part within the recess 300 in the recess 300, an inert gas is supplied into the processing chamber 201 from the nozzles 249a to 249c respectively, and exhausted from the exhaust port 231a. The inert gas supplied from the nozzles 249a to 249c acts as a purge gas, whereby the inside of the processing chamber 201 is purged, and the gas, reaction by-products, etc. remaining in the processing chamber 201 are removed from the processing chamber 201.

[0175] 〔Step C (Selective growth, bottom-up growth)〕

[0176] After step B is completed and the inside of the processing chamber 201 is purged, step C is carried out. In step C, a film formation gas is supplied to the wafer 200, so that as Figure 4 shown in (d) of Figure 5 shown in (d) of

[0177] For example, in this step, by alternately supplying a source gas and a reaction gas as film-forming gases to the wafer 200, the film 308 can be grown starting from the portion of the base film 304 formed in the recess 300 where the film-forming inhibition layer 306 is not formed. That is, in this step, by performing a cycle of alternately supplying the source gas and the reaction gas to the wafer 200 a specified number of times (n times, where n is an integer of 1 or more), the film 308 can be grown from the bottom to the top in the recess 300 starting from the portion of the base film 304 formed in the recess 300 where the film-forming inhibition layer 306 is not formed, that is, the bottom of the base film 304 formed in the recess 300. In this case, it is preferable to interpose a purge of the processing chamber 201 with an inert gas between these steps. That is, in this step, it is preferable to perform a cycle of alternately performing the following steps a specified number of times (n times, where n is an integer of 1 or more): a step of supplying a source gas to the wafer 200; a step of purging the processing chamber 201; a step of supplying a reaction gas; and a step of purging the processing chamber 201. In addition, a catalyst gas may be supplied together with at least one of the source gas and the reaction gas. In this case, the processing temperature can be lowered, and film formation at room temperature can be achieved. The processing timing of this step can be expressed as follows, and any one of the following four processing timings can be performed.

[0178] (Source gas → Purge → Reaction gas → Purge) × n

[0179] (Source gas + Catalyst gas → Purge → Reaction gas → Purge) × n

[0180] (Source gas → Purge → Reaction gas + Catalyst gas → Purge) × n

[0181] (Source gas + Catalyst gas → Purge → Reaction gas + Catalyst gas → Purge) × n

[0182] When using a source gas as the film-forming gas, the valve 243a is opened, and the source gas is supplied into the gas supply pipe 232a. The flow rate of the source gas is adjusted by the MFC241a, supplied into the processing chamber 201 via the nozzle 249a, and exhausted from the exhaust port 231a. At this time, the source gas is supplied to the wafer 200. At this time, the valves 243e to 243g may be opened, and inert gases may be supplied into the processing chamber 201 via the nozzles 249a to 249c, respectively.

[0183] When using a reactive gas as the film-forming gas, valve 243b is opened to supply the reactive gas into gas supply pipe 232b. The reactive gas is flow-regulated by MFC241b, supplied into processing chamber 201 via nozzle 249b, and exhausted from exhaust port 231a. At this time, the reactive gas is supplied to wafer 200. At this time, valves 243e - 243g can also be opened to supply inert gases into processing chamber 201 via nozzles 249a - 249c respectively.

[0184] When using a catalyst gas as the film-forming gas, valve 243c is opened to supply the catalyst gas into gas supply pipe 232c. The catalyst gas is flow-regulated by MFC241c, supplied into processing chamber 201 via nozzle 249c, and exhausted from exhaust port 231a. At this time, the catalyst gas is supplied to wafer 200. At this time, valves 243e - 243g can also be opened to supply inert gases into processing chamber 201 via nozzles 249a - 249c respectively.

[0185] When alternately supplying a source gas and a reactive gas and purging the inside of processing chamber 201 with an inert gas between them, valves 243e - 243g are opened to supply inert gases into gas supply pipes 232e - 232g respectively. The inert gases are flow-regulated by MFC241e - 241g, supplied into processing chamber 201 via nozzles 249a - 249c, and exhausted from exhaust port 231a. At this time, the inside of processing chamber 201 is purged with the inert gas.

[0186] Examples of the processing conditions when supplying the source gas in this step are as follows:

[0187] Processing temperature: room temperature (25°C) to 600°C, preferably 50 to 550°C

[0188] Processing pressure: 1 to 2000 Pa, preferably 10 to 1333 Pa

[0189] Source gas supply flow rate: 1 to 2000 sccm, preferably 10 to 1000 sccm

[0190] Source gas supply time: 1 to 180 seconds, preferably 10 to 120 seconds

[0191] Catalyst gas supply flow rate: 0 to 2000 sccm

[0192] Inert gas supply flow rate (for each gas supply pipe): 0 to 20000 sccm.

[0193] Examples of the processing conditions when supplying the reactive gas in this step are as follows:

[0194] Processing temperature: room temperature (25 °C) to 600 °C, preferably 50 to 550 °C

[0195] Processing pressure: 1 to 5000 Pa, preferably 10 to 3000 Pa

[0196] Reaction gas supply flow rate: 1 to 20000 sccm, preferably 10 to 2000 sccm

[0197] Reaction gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds

[0198] Catalyst gas supply flow rate: 0 to 2000 sccm

[0199] Inert gas supply flow rate (for each gas supply pipe): 0 to 20000 sccm.

[0200] As the processing conditions for purging the inside of the processing chamber 201 in this step, the following can be exemplified:

[0201] Processing temperature: room temperature (25 °C) to 600 °C, preferably 50 to 550 °C

[0202] Processing pressure: 1 to 10 Pa, preferably 1 to 20 Pa

[0203] Inert gas supply flow rate (for each gas supply pipe): 500 to 20000 sccm

[0204] Inert gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds.

[0205] As the raw material gas, for example, the above-mentioned halosilane gases such as chlorosilane gases, fluorosilane gases, bromosilane gases, and iodosilane gases, and aminosilane gases exemplified in the description of step A can be used. As the raw material gas, in addition, for example, 1,1,2,2-tetrachloro-1,2-dimethylethylsilane ((CH 3 ) 2 Si 2 Cl 4 , abbreviation: TCDMDS) gas, 1,2-dichloro-1,1,2,2-tetramethylethylsilane ((CH 3 ) 4 Si 2 Cl 2 , abbreviation: DCTMDS) gas and other alkyl halosilane (alkyl chlorosilane) gases, bis(trichlorosilyl)methane ((SiCl 3 ) 2 CH 2 , abbreviation: BTCSM) gas, 1,2-bis(trichlorosilyl)ethane ((SiCl 3 ) 2 C2 H 4 ., abbreviation: BTCSE) gas, 1,1,3,3 - tetrachloro - 1,3 - disilacyclobutane (C 2 H 4 Cl 4 Si 2 ., abbreviation: TCDSCB) gas and other alkyl chlorosilane gases. That is, as halogenated silane (chlorosilane) gases, halogenated silane (chlorosilane) gases containing a hydrocarbon group, i.e., containing C, can also be used. As the raw material gas, one or more of them can be used.

[0206] As the reaction gas, for example, the above - mentioned oxidation gas (O - containing gas) exemplified in the description of step A can be used. As the reaction gas, in addition, for example, ammonia (NH 3 ) gas, hydrazine (N 2 H 4 ) gas, diazene (N 2 H 2 ) gas, N 3 H 8 gas and other nitrogen - containing gases containing N - H bonds (N - and H - containing gases) can be used. As the reaction gas, one or more of them can be used.

[0207] As the catalyst gas, for example, amine gases containing C, N, and H can be used. As the amine gas, for example, pyridine gas (C 5 H 5 N, abbreviation: py) gas, aminopyridine (C 5 H 6 N 2 ) gas, methylpyridine (C 6 H 7 N) gas, dimethylpyridine (C 7 H 9 N) gas, piperazine (C 4 H 10 N 2 ) gas, piperidine (C 5 H 11 N) gas and other cyclic amine gases, triethylamine ((C 2 H 5 ) 3 N, abbreviation: TEA) gas, diethylamine ((C 2 H 5 ) 2 NH, abbreviation: DEA) gas and other chain - like amine gases, etc.

[0208] By supplying a source gas (+ catalyst gas) to the wafer 200 using the above-mentioned respective gases under the above-mentioned processing conditions, a Si-containing layer is formed on the surface of the region in the base film 304 formed in the recess 300 where the film formation inhibiting layer 306 is not formed. That is, the Si-containing layer is formed starting from the region in the base film 304 formed in the recess 300 where the film formation inhibiting layer 306 is not formed, that is, the region in the base film 304 corresponding to the bottom in the recess 300.

[0209] In this step, it is possible to selectively form a Si-containing layer on the surface of the region in the base film 304 where the film formation inhibiting layer 306 is not formed while suppressing the formation of a Si-containing layer on the surface of the region in the base film 304 where the film formation inhibiting layer 306 is formed. It should be noted that in the case where the film formation inhibiting effect caused by the film formation inhibiting layer 306 becomes insufficient for some reason, there is also a case where a Si-containing layer is formed in a very small amount on the surface of the region in the base film 304 where the film formation inhibiting layer 306 is formed. In this case, the thickness of the Si-containing layer formed on the surface of the region in the base film 304 where the film formation inhibiting layer 306 is formed is much thinner than the thickness of the Si-containing layer formed on the surface of the region in the base film 304 where the film formation inhibiting layer 306 is not formed. The reason why such selective formation of the Si-containing layer can be achieved is that the F-terminated or hydrocarbon group-terminated groups present on the surface of the region in the base film 304 where the film formation inhibiting layer 306 is formed hinder the formation of a Si-containing layer (adsorption of Si) on the surface of the region in the base film 304 where the film formation inhibiting layer 306 is formed, that is, they act as a film formation inhibitor. It should be noted that the F-terminated or hydrocarbon group-terminated groups present on the surface of the region in the base film 304 where the film formation inhibiting layer 306 is formed can also be stably maintained without disappearing when this step is carried out. It should be noted that depending on the processing conditions, there is also the following situation: as the above cycle is repeated, the F-terminated or hydrocarbon group-terminated groups present on the surface of the region where the film formation inhibiting layer 306 is formed gradually detach.

[0210] Using each of the above gases, by supplying, for example, a nitriding gas (+ catalyst gas) as a reaction gas to the wafer 200 under the above processing conditions, at least a part of the Si-containing layer formed on the surface of the region in the base film 304 formed in the recess 300 where the film formation inhibiting layer 306 is not formed is nitrided (modified). By nitriding the Si-containing layer, a layer containing Si and N, that is, a silicon nitride layer (SiN layer), is formed on the surface of the region in the base film 304 where the film formation inhibiting layer 306 is not formed. It should be noted that, with respect to the surface of the region in the base film 304 where the film formation inhibiting layer 306 is formed, it is maintained without being nitrided when this step is carried out. That is, the surface of the region in the base film 304 where the film formation inhibiting layer 306 is formed is stably maintained in a state capped with F or a hydrocarbon group without being nitrided. It should be noted that, depending on the processing conditions, there may also be a case where the F capping or hydrocarbon group capping present on the surface of the region where the film formation inhibiting layer 306 is formed gradually detaches as the above cycle is repeated.

[0211] By supplying, for example, a nitriding gas + an oxidizing gas (+ catalyst gas) as a reaction gas to the wafer 200 under the above conditions, at least a part of the Si-containing layer formed on the surface of the region in the base film 304 formed in the recess 300 where the film formation inhibiting layer 306 is not formed is oxynitrided (modified). By oxynitriding the Si-containing layer, a layer containing Si, O, and N, that is, a silicon oxynitride layer (SiON layer), is formed on the surface of the region in the base film 304 where the film formation inhibiting layer 306 is not formed. It should be noted that, with respect to the surface of the region in the base film 304 where the film formation inhibiting layer 306 is formed, it is maintained without being oxynitrided when this step is carried out. That is, the surface of the region in the base film 304 where the film formation inhibiting layer 306 is formed is stably maintained in a state capped with F or a hydrocarbon group without being oxynitrided. It should be noted that, depending on the processing conditions, there may also be a case where the F capping or hydrocarbon group capping present on the surface of the region where the film formation inhibiting layer 306 is formed gradually detaches as the above cycle is repeated.

[0212] By repeating the cycle of non-simultaneously, that is, asynchronously, performing the step of supplying the source gas to the wafer 200 and the step of supplying the reaction gas to the wafer 200 a specified number of times (n times, n is an integer of 1 or more), it is possible to selectively grow, for example, a silicon nitride film (SiN film) or a silicon oxynitride film (SiON film) as the film 308 on the surface of the region in the base film 304 formed in the recess 300 on the surface of the wafer 200 starting from the region where the film formation inhibiting layer 306 is not formed. And by repeating this cycle, as in Figure 4 (d) to Figure 4 (g) of Figure 5 (d) to Figure 5As shown in (i) of , as the film 308, for example, a SiN film or a SiON film can grow upward from the bottom in the recess 300 from bottom to top. It is preferable that the above cycle is repeated multiple times. That is, it is preferable that the thickness of the SiN layer or the SiON layer formed in each cycle is thinner than the desired film thickness, and the above cycle is repeated multiple times until the film thickness of the film 308 formed by laminating the SiN layer or the SiON layer reaches the desired film thickness.

[0213] It should be noted that it is preferable that, in the later stage of film formation, such as Figure 4 in (e) of to Figure 4 in (g) of , Figure 5 in (g) of to Figure 5 as shown in (i) of , before the film 308 grows to the upper part in the recess 300, the film formation inhibiting layer 306 (F capping layer, hydrocarbon group capping layer) is removed and / or invalidated by the action of the film formation gas (raw material gas, reaction gas, etc.). Thereby, the surface state of the region of the base film 304 in the recess 300 where the film formation inhibiting layer 306 is formed can be reset. Here, the invalidation of the film formation inhibiting layer 306 means that chemical changes such as the molecular structure of the film formation inhibiting layer 306 formed on the surface of the base film 304 and the arrangement structure of atoms on the surface of the film formation inhibiting layer 306 can be achieved, the adsorption of the film formation gas (raw material gas, reaction gas, etc.) to the surface of the base film 304 can be realized, and the reaction between the surface of the base film 304 and the film formation gas (raw material gas, reaction gas, etc.) can be carried out.

[0214] For example, by previously forming the film formation inhibiting layer 306 that undergoes selective destruction in the later stage of film formation in step B, the above effect can be achieved. Specifically, for example, by previously forming the film formation inhibiting layer 306 that detaches and disappears in the later stage of film formation in step B, the above effect can be achieved. Additionally, for example, by previously forming the film formation inhibiting layer 306 whose film formation inhibiting effect disappears in the later stage of film formation in step B, the above effect can be achieved. Further, for example, by previously forming the film formation inhibiting layer 306 whose film formation inhibiting effect is insufficient or limited in the later stage of film formation in step B, the above effect can be achieved. It should be noted that for the above film formation inhibiting layer 306, by previously obtaining the relationship between each processing condition (processing temperature, processing pressure, film formation inhibitor supply flow rate, film formation inhibitor supply time) in step B and the number of cycles in step C until selective destruction occurs, etc., the above film formation inhibiting layer 306 can be appropriately formed based on this relationship. Thereby, the film formation inhibiting layer 306 and the components constituting the film formation inhibiting layer 306 can be inhibited from being taken into the interface between the base film 304 and the film 308.

[0215] In addition, for example, by performing Step C under the processing conditions of at least any one of the removal and invalidation of the film formation inhibiting layer 306 in the latter stage of film formation, the above-described effects can be achieved. Specifically, for example, by supplying a reaction gas to the wafer 200 under the processing conditions in which the film formation inhibiting layer 306 detaches and disappears in the latter stage of film formation, the above-described effects can be achieved. In addition, for example, by supplying a reaction gas to the wafer 200 under the processing conditions in which the film formation inhibiting effect caused by the film formation inhibiting layer 306 disappears in the latter stage of film formation, the above-described effects can be achieved. In addition, for example, by supplying a reaction gas to the wafer 200 under the processing conditions in which the film formation inhibiting effect caused by the film formation inhibiting layer 306 is reduced in the latter stage of film formation, the above-described effects can be achieved. For example, by making at least any one of the processing temperature, processing pressure, and reaction gas supply flow rate when supplying the reaction gas to the wafer 200 in the latter stage of film formation greater than or equal to the corresponding amounts in the early stage and middle stage of film formation, the oxidizing power or nitriding power brought by the reaction gas can be increased, and such processing conditions can be achieved. In addition, for example, by making the reaction gas supply time when supplying the reaction gas to the wafer 200 in the latter stage of film formation greater than or equal to the corresponding time in the early stage and middle stage of film formation, the oxidation time or nitriding time based on the reaction gas can be increased, and such processing conditions can be achieved. Thereby, it is possible to suppress the film formation inhibiting layer 306 and the components constituting the film formation inhibiting layer 306 from being taken into the interface between the base film 304 and the film 308.

[0216] In these cases, when the film 308 is a SiON film, as the reaction gas supplied in the latter stage of film formation, for example, an oxidizing gas such as an O-containing gas, an O-containing gas + an H-containing gas, etc. is preferably used. In this case, the oxidizing gas can also be plasma-excited and supplied. When supplying the oxidizing gas into the processing chamber 201, by applying RF power to the RPU 502, the oxidizing gas can be plasma-excited and supplied. In this case, at least any one of the removal and invalidation of the film formation inhibiting layer 306 can be performed efficiently and effectively. It should be noted that in this case, when it is necessary to maintain the composition of the film 308, it is preferable to plasma-excite and supply the oxidizing gas under the condition that N does not detach from the film 308.

[0217] In addition, when the film 308 is a SiN film, as the reaction gas supplied in the latter stage of film formation, for example, a nitriding gas such as an N- and H-containing gas is preferably used. In this case, the nitriding gas can also be plasma-excited and supplied. When supplying the nitriding gas into the processing chamber 201, by applying RF power to the RPU 502, the nitriding gas can be plasma-excited and supplied. In this case, at least any one of the removal and invalidation of the film formation inhibiting layer 306 can be performed efficiently and effectively.

[0218] It should be noted that the formation of the film formation inhibitor layer 306 removed in the later stage of film formation, the formation of the film formation inhibitor layer 306 invalidated in the later stage of film formation, the removal of the film formation inhibitor layer 306 in the later stage of film formation, the invalidation of the film formation inhibitor layer 306 in the later stage of film formation, etc. can be carried out in the same manner in the second embodiment described later.

[0219] It should be noted that as Figure 5 (d) of Figure 5 (f) of shows, there are also cases where the film formation inhibitor layer 306 (F capping layer, hydrocarbon capping layer) is removed and / or invalidated by the action of the film formation gas (raw material gas, reaction gas, etc.) during the film formation process. For example, when an oxidizing gas such as an O-containing gas + an H-containing gas is used as the reaction gas, there are cases where the film formation inhibitor layer 306 detaches due to high oxidizing power, the film formation inhibition effect in the film formation inhibitor layer 306 disappears, decreases, etc. In this case, as Figure 5 (e) of Figure 5 (g) of shows, it is only necessary to perform step B again to repair the film formation inhibitor layer 306 or to form the film formation inhibitor layer 306 again.

[0220] In addition, as shown in the following processing time sequence, the film formation inhibitor can also be supplied each time before the cycle in step C to form the film formation inhibitor layer 306. In this case, any one of the following four processing time sequences can be carried out. It should be noted that for convenience, only step B and step C in the following processing time sequence are extracted for explanation.

[0221] (Film formation inhibitor → Purge → Raw material gas → Purge → Reaction gas → Purge) × n

[0222] (Film formation inhibitor → Purge → Raw material gas + Catalyst gas → Purge → Reaction gas → Purge) × n

[0223] (Film formation inhibitor → Purge → Raw material gas → Purge → Reaction gas + Catalyst gas → Purge) × n

[0224] (Film formation inhibitor → Purge → Raw material gas + Catalyst gas → Purge → Reaction gas + Catalyst gas → Purge) × n

[0225] According to this processing timing, it is possible to repair or form the film formation inhibiting layer 306 removed and / or invalidated in step C in each cycle. For example, as described above, it is particularly effective when using an oxidation gas with high oxidizing power. In this case, it is preferable that the material of the base film 304 is different from the material of the film 308. This is because, when the material of the base film 304 is the same as the material of the film 308, starting from the second cycle, there is a case where the film formation inhibiting layer 306 is also formed on the surface of the film 308 (or the layer constituting the film 308) formed in the first cycle and film formation becomes impossible thereafter.

[0226] In addition, when selective damage occurs during film formation, there is also a case where the base film 304 is etched. For example, when selective damage occurs, there is a case where the film 308 is formed on the surface of the region of the base film 304 where the film formation inhibiting layer 306 is formed. In this case, it is necessary to remove the film 308 formed on the surface of the region of the base film 304 where the film formation inhibiting layer 306 is formed by an etching process using an F-containing gas or the like. However, at this time, there is a case where the base film 304 is also etched. In such a case, as shown in the following processing timing, it is only necessary to perform step A again and repair the base film 304 or form the base film 304 again. In this case, the process performed in step A and the processes of performing step B and step C a specified number of times (m 1 times, m 1 is an integer of 1 or more) are performed a specified number of times (m 2 times, m 2 is an integer of 1 or more).

[0227] 〔Step A → (Step B → Step C) × m 1 〕× m 2

[0228] It should be noted that regarding the repair of the film formation inhibiting layer 306, the reformation of the film formation inhibiting layer 306, the repair of the base film 304, the reformation of the base film 304, and each processing timing for performing these processes, they can be similarly performed in the second embodiment described later.

[0229] (Post-purge and atmospheric pressure recovery)

[0230] As Figure 4 in (g), Figure 5As shown in (i) of , after the embedding in the recess 300 of the film 308 is completed, an inert gas as a purge gas is supplied into the processing chamber 201 from the nozzles 249a to 249c, respectively, and exhausted from the exhaust port 231a. Thereby, the inside of the processing chamber 201 is purged, and gases, reaction by-products, etc. remaining in the processing chamber 201 are removed from the processing chamber 201 (post-purge). After that, the atmosphere inside the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure inside the processing chamber 201 is restored to normal pressure (atmospheric pressure restoration).

[0231] (Cassette unloading and wafer unloading)

[0232] After that, the seal cover 219 is lowered by the cassette elevator 115, and the lower end of the manifold 209 is opened. And the processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 in a state of being supported by the cassette 217 (cassette unloading). After the cassette unloading, the gate 219s is moved, and the lower end opening of the manifold 209 is sealed by the gate 219s with the O-ring 220c (gate closing). After the processed wafer 200 is carried out to the outside of the reaction tube 203, it is removed from the cassette 217 (wafer unloading).

[0233] It should be noted that in a state where the recess 300 is filled with the film 308, the SiO film formed as the base film 304 remains at the interface between the surface inside the recess 300 and the film 308. However, if the thickness of the SiO film formed as the base film 304 is, for example, below the thickness of the native oxide film level of (1 to 2 nm) or less, there is no problem. In addition, the thickness of the SiO film formed as the base film 304 may be thicker than the thickness of the native oxide film level, and when it is a process or device that can tolerate this thickness, this technology can be used.

[0234] (3) Effects of this method

[0235] According to this method, one or more of the following effects can be obtained.

[0236] In step A, the base film 304 having a higher reactivity with the film formation inhibitor than the reactivity of the film formation inhibitor with the surface inside the recess 300 is formed inside the recess 300 provided on the surface of the wafer 200, so that a film formation inhibiting layer 306 having a high film formation inhibiting effect and being appropriate can be selectively and efficiently formed at a high density in a portion corresponding to the upper part inside the recess 300, and the filling characteristics can be improved. Thereby, seamless and hole-free gap filling can be achieved.

[0237] By forming an O-containing film as the base film 304 in step A, it is possible to selectively and efficiently form, at a high density, a film-forming inhibition layer 306 with a high film-forming inhibition effect and appropriate properties at a portion corresponding to the upper part within the recess 300 provided on the surface of the wafer 200, and the embedding characteristics can be further improved.

[0238] By forming an oxygen film as the base film 304 in step A, it is possible to selectively and efficiently form, at a high density, a film-forming inhibition layer 306 with a high film-forming inhibition effect and appropriate properties at a portion corresponding to the upper part within the recess 300 provided on the surface of the wafer 200, and the embedding characteristics can be further improved.

[0239] By forming a Si- and O-containing film as the base film 304 in step A, it is possible to selectively and efficiently form, at a high density, a film-forming inhibition layer 306 with a high film-forming inhibition effect and appropriate properties at a portion corresponding to the upper part within the recess 300 provided on the surface of the wafer 200, and the embedding characteristics can be further improved.

[0240] By forming a SiO film as the base film 304 in step A, it is possible to selectively and efficiently form, at a high density, a film-forming inhibition layer 306 with a high film-forming inhibition effect and appropriate properties at a portion corresponding to the upper part within the recess 300 provided on the surface of the wafer 200, and the embedding characteristics can be further improved.

[0241] By forming the base film 304 throughout the recess 300 in step A, there is no need to selectively form the base film 304 at a specific portion, and thus the control during the formation of the base film 304 can be simplified.

[0242] By alternately supplying a source gas and a modifying gas as a pretreatment gas in step A, the base film 304 is deposited within the recess 300, or the surface within the recess 300 is modified by supplying a modifying gas as a pretreatment gas to form the base film 304 within the recess 300, so that a uniform base film 304 can be formed over the entire range within the recess.

[0243] By forming the base film 304 throughout the recess 300 in step A, it is possible to prevent the surface within the recess 300 from being exposed to reactive substances in subsequent steps, and the surface within the recess 300 can be protected from chemical and physical actions.

[0244] By using a fluorine-containing gas as a film formation inhibitor in step B, an F-capped layer can be formed as the film formation inhibition layer 306, and a film formation inhibition layer 306 with a high film formation inhibition effect and appropriate properties can be selectively and efficiently formed at a high density on the portion corresponding to the upper part in the recess 300 on the surface of the wafer 200, and the embedding property can be further improved. It should be noted that in this case, as the film formation gas (raw material gas, reaction gas, etc.), a gas other than the O- and H-containing gas is preferably used. This is because when an O- and H-containing gas is used as the reaction gas, for example, the F-capped layer formed as the film formation inhibition layer 306 may peel off. In this case, as the reaction gas, a nitriding gas such as an N- and H-containing gas is preferably used. It should be noted that as described above, when the film formation inhibition layer 306 peels off or disappears in the later stage of film formation, an O- and H-containing gas can be used as the reaction gas. In addition, as described above, when the film formation inhibition layer 306 peels off or disappears, if the film formation inhibition layer 306 is appropriately reformed, an O- and H-containing gas can be used as the reaction gas.

[0245] By using a hydrocarbon group-containing gas as a film formation inhibitor in step B, a hydrocarbon group-capped layer can be formed as the film formation inhibition layer 306, and a film formation inhibition layer 306 with a high film formation inhibition effect and appropriate properties can be selectively and efficiently formed at a high density on the portion corresponding to the upper part in the recess 300 on the surface of the wafer 200, and the embedding property can be further improved. It should be noted that in this case, for example, since the hydrocarbon group-capped layer formed as the film formation inhibition layer 306 peels off at a temperature of 500 °C or higher, film formation is preferably performed at a temperature lower than this temperature. In this case, for example, in order to lower the processing temperature in step C, a catalyst gas is preferably supplied together with at least one of the raw material gas and the reaction gas. Thus, for example, the processing temperature can also be from room temperature to 200 °C, and further can be from room temperature to 120 °C.

[0246] <Second Embodiment in the Present Invention>

[0247] Hereinafter, mainly with reference to Figures 1 to 3 、 Figures 6 to 9 the second embodiment in the present invention will be described. It should be noted that the configuration of the substrate processing apparatus in the second embodiment is the same as that of the substrate processing apparatus in the first embodiment described above, and other aspects in the second embodiment except for the aspects described later are the same as those in the first embodiment described above. Hereinafter, the substrate processing process in the second embodiment will be described.

[0248] Here, mainly using Figure 6 of (a) to Figure 6 of (g), Figure 7 of (a) to Figure 7(i) An example of the following process is described: Using the above-described substrate processing apparatus, as one process of the manufacturing process of a semiconductor device, a film is grown from the bottom up in recesses such as grooves and holes provided on the surface of the wafer 200. In the following description, the operations of the respective parts constituting the substrate processing apparatus are controlled by the controller 121.

[0249] In Figure 6 of (a) - Figure 6 of (g), Figure 7 of (a) - Figure 7 In the processing timings shown in (i), the following steps A, B, and C are performed, and after performing the following step A, the following step B and the following step C are performed a specified number of times (m times, where m is an integer of 1 or more):

[0250] Step A, in which a pre-treatment gas is supplied to the wafer 200 having recesses 300 on its surface, thereby forming a base film 304 in at least the upper part of the recesses 300, the reactivity of which with the film formation inhibitor is higher than the reactivity of the film formation inhibitor with the surface of the recesses 300.

[0251] Step B, in which a film formation inhibitor is supplied to the wafer 200, thereby forming a film formation inhibiting layer 306 in a portion corresponding to the upper part of the recesses 300 on the surface of the base film 304 formed in at least the upper part of the recesses 300.

[0252] Step C, in which a film formation gas is supplied to the wafer 200, thereby growing a film 308 starting from a portion where the film formation inhibiting layer 306 is not formed in the recesses 300.

[0253] In the present embodiment, similarly to the above-described first embodiment, step A is also referred to as base film formation, step B is also referred to as film formation inhibiting layer formation, and step C is also referred to as selective growth (selective film formation) or bottom-up growth (bottom-up film formation). The above-described processing timings can be expressed as follows, similarly to the above-described first embodiment.

[0254] Step A → (Step B → Step C) × m

[0255] Here, the case where m = 1 corresponds to the processing timings shown in (a) - Figure 6 of Figure 6 of (g), and the case where m > 1, that is, the case where m ≥ 2, corresponds to the processing timings shown in (a) - Figure 7 of Figure 7 of (i). In the processing timings shown in (a) - Figure 7 of Figure 7 of (i), the case where m = 3 is exemplified. The case where m = 1, that is, Figure 6 of (a) - Figure 6 of (g) can also be shown as follows.

[0256] Step A → Step B → Step C

[0257] It should be noted that Figure 6 (a) to Figure 6 (g) of Figure 7 (a) to Figure 7 (i) of the processing timing shows an example in which the base film 304 is selectively formed on the upper part in the recess 300 in Step A and the film formation inhibiting layer 306 is formed on the entire base film 304 in Step B. In this case, as a result, the film formation inhibiting layer 306 is formed in the portion corresponding to the upper part in the recess 300.

[0258] The wafer loading, boat loading, pressure regulation, temperature regulation, post purge, and atmospheric pressure recovery in this embodiment can be carried out in the same manner as each process in the above-described first embodiment. Hereinafter, Step A, Step B, and Step C in this embodiment will be described.

[0259] [Step A (Base Film Formation)]

[0260] In this step, a pretreatment gas is supplied to the wafer 200 so as to selectively (preferably) form a base film 304 having a higher reactivity with the film formation inhibitor than the reactivity of the film formation inhibitor with the surface in the recess 300 at least on the upper part in the recess 300, here as shown in Figure 6 (b) of Figure 7 (b) of Figure 8 the upper part in the recess 300.

[0261] For example, in this step, as the pretreatment gas, by supplying the source gas (+ modifier gas) to the wafer 200 under conditions where a gas-phase reaction predominantly occurs, the base film 304 can be selectively deposited on the upper part within the recess 300 (Method 2-A1). Alternatively, by alternately supplying the source gas and the modifier gas as the pretreatment gas under conditions where the source gas and / or the modifier gas are consumed and / or deactivated in the upper part within the recess 300, the base film 304 can be selectively deposited on the upper part within the recess 300 (Method 2-A2). Alternatively, by supplying the pretreatment gas under conditions where the step coverage deteriorates, depositing the base film 304 within the recess 300, and then supplying the etching gas under conditions where the base film 304 can be etched conformally, the base film 304 can be left on the upper part within the recess 300 and the surface of the part other than the upper part within the recess 300 can be exposed (Method 2-A3). Alternatively, as the pretreatment gas, by supplying the modifier gas under conditions where the modifier gas is consumed and / or deactivated in the upper part within the recess 300, the upper surface within the recess 300 can be selectively modified, and the base film 304 can be selectively formed on the upper part within the recess 300 (Method 2-A4). It should be noted that the material of the base film 304 in this embodiment is the same as that in the above-described first embodiment.

[0262] When forming an SiO film as the base film 304, similar to the above-described first embodiment, an oxidation gas can be used as the modifier gas. As the source gas, in addition to the above-described source gas, an O-containing source gas can be used.

[0263] That is, in this case, for example, by supplying the source gas (+ oxidation gas) to the wafer 200 as the pretreatment gas under conditions where a gas-phase reaction predominantly occurs, as shown in Figure 6 (b) of Figure 7 (b) of Figure 8 , as the base film 304, an SiO film can be selectively deposited on the upper part within the recess 300 (Method 2-A1).

[0264] In addition, for example, as the pretreatment gas, by alternately supplying the source gas and the oxidation gas (modifier gas) under conditions where the source gas and / or the oxidation gas are consumed and / or deactivated in the upper part within the recess 300, as shown in Figure 6 (b) of Figure 7 (b) of Figure 8 , as the base film 304, an SiO film can be selectively deposited on the upper part within the recess 300 (Method 2-A2).

[0265] In this case, it is preferable to interpose a purge in the processing chamber 201 with an inert gas therebetween. Additionally, an oxidation gas plasma can be excited and supplied. Further, a catalyst gas can be supplied together with at least any one of the source gas and the oxidation gas. In these cases, it is possible to achieve a lower processing temperature and also to form a film at room temperature.

[0266] Further, for example, when a pretreatment gas is supplied under conditions where the step coverage deteriorates, as Figure 9 shown in (a) of, after depositing a SiO film in the recess 300 as the base film 304, an etching gas is supplied under conditions where the base film 304 can be etched conformally, so that as Figure 6 shown in (b) of, Figure 7 shown in (b) of, Figure 9 shown in (b) of, a SiO film remains on the upper part in the recess 300 as the base film 304, and the surface of the portion other than the upper part in the recess 300 can be exposed (Method 2-A3).

[0267] Further, for example, as a pretreatment gas, by supplying an oxidation gas (modifying gas) under conditions where the oxidation gas is consumed and / or deactivated in the upper part in the recess 300, so that as Figure 6 shown in (b) of, Figure 7 shown in (b) of, Figure 8 shown, the surface of the upper part in the recess 300 can be selectively oxidized (modified), and a SiO film can be selectively formed on the upper part in the recess 300 as the base film 304 (Method 2-A4).

[0268] The method of supplying the source gas, the oxidation gas, the catalyst gas, and the inert gas, and the method of purging the inside of the processing chamber 201 are the same as the corresponding methods in the above-described first embodiment. It should be noted that when supplying the oxidation gas into the processing chamber 201, the oxidation gas plasma can be excited and supplied by applying RF power to the RPU 502.

[0269] In this step, according to Method 2-A1, the processing conditions when supplying the source gas (+ oxidation gas) in the case of forming a SiO film as the base film 304 can be exemplified as follows:

[0270] Processing temperature: 500 to 750 °C

[0271] Processing pressure: 1 to 1000 Pa, preferably 10 to 500 Pa

[0272] Source gas supply flow rate: 10 to 1000 sccm, preferably 100 to 500 sccm

[0273] Source gas supply time: 1 to 60 minutes, preferably 1 to 30 minutes

[0274] Oxidizing gas supply flow rate: 0 - 500 sccm, preferably 0 - 300 sccm

[0275] Inert gas supply flow rate (for each gas supply pipe): 0 - 20000 sccm.

[0276] The processing conditions can also be processing conditions with strong CVD (Chemical Vapor Deposition) behavior. In this case, as the source gas, for example, tetraethoxysilane (Si(OCH 2 CH 3 ) 4 , abbreviation: TEOS) gas and other O-containing source gases can be used. In this case, the O-containing source gas can be used alone to deposit the SiO film, but the O-containing source gas + oxidizing gas can also be used. In addition, a source gas without O + oxidizing gas can also be used. In this case, as the source gas without O, in addition to the source gas in the above first embodiment, monosilane (SiH 4 ) gas, disilane (Si 2 H 6 ) gas and other silicon hydride gases can also be used. As the oxidizing gas, the oxidizing gas in the above first embodiment can be used.

[0277] In this step, according to Method 2-A2, the processing conditions for supplying the source gas when forming the SiO film on the base film 304 can be exemplified as follows:

[0278] Processing temperature: room temperature (25°C) - 700°C, preferably 200 - 650°C

[0279] Processing pressure: 1 - 2000 Pa, preferably 5 - 1000 Pa

[0280] Source gas supply flow rate: 1 - 3000 sccm, preferably 1 - 500 sccm

[0281] Source gas supply time: 1 - 120 seconds, preferably 1 - 60 seconds

[0282] Catalyst gas supply flow rate: 0 - 2000 sccm

[0283] Inert gas supply flow rate (for each gas supply pipe): 0 - 20000 sccm.

[0284] As the source gas and catalyst gas, the same gases as the source gas and catalyst gas in the above first embodiment can be used respectively.

[0285] In this step, according to Method 2-A2, the processing conditions for supplying the oxidation gas when forming the SiO film on the base film 304 can be exemplified as follows:

[0286] Processing temperature: room temperature (25°C) to 700°C, preferably 200 to 650°C

[0287] Processing pressure: 1 to 4000 Pa, preferably 1 to 3000 Pa

[0288] Oxidation gas supply flow rate: 1 to 10000 sccm, preferably 100 to 2000 sccm

[0289] Oxidation gas supply time: 0.1 to 10 seconds, preferably 1 to 10 seconds

[0290] Catalyst gas supply flow rate: 0 to 2000 sccm

[0291] Inert gas supply flow rate (for each gas supply pipe): 0 to 20000 sccm

[0292] High-frequency power (RF power): 0 to 1500 W.

[0293] As the oxidation gas and the catalyst gas, the same gases as the oxidation gas and the catalyst gas in the above-described first embodiment can be used respectively.

[0294] In this case, the oxidation gas can be supplied in a non-plasma atmosphere, or the oxidation gas can be plasma-excited and supplied. It should be noted that high-frequency power (RF power): 0 W means that plasma is not used, that is, non-plasma. When the oxidation gas is plasma-excited and supplied, the oxidation gas is supplied under the condition that the O-containing radicals generated by plasma-exciting the oxidation gas are consumed and / or deactivated in the upper part of the concave portion 300. It should be noted that here, the processing conditions for supplying the oxidation gas under the condition that the oxidation gas is consumed and / or deactivated in the upper part of the concave portion 300 are exemplified, but the raw material gas can also be supplied under the condition that the raw material gas is consumed and / or deactivated in the upper part of the concave portion 300.

[0295] In this step, according to Method 2-A3, for the pretreatment gas, processing method, and processing conditions when forming the SiO film on the base film 304 under the condition of poor step coverage, the pretreatment gas, processing method, and processing conditions of the above Method 2-A1 or Method 2-A2 can be used. It should be noted that in Method 2-A3, for example, the supply time of the raw material gas and the supply time of the reaction gas can be made longer than the supply time of the raw material gas and the supply time of the reaction gas in the above Method 2-A1 and Method 2-A2.

[0296] In this step, according to Method 2-A3, the processing conditions for using an F-containing gas as an etching gas and conformally etching the base film 304 after forming the SiO film as the base film 304 can be exemplified as follows:

[0297] Processing temperature: room temperature (25 °C) to 300 °C

[0298] Processing pressure: 1 to 1000 Pa, preferably 10 to 500 Pa

[0299] F-containing gas supply flow rate: 10 to 1000 sccm, preferably 100 to 500 sccm

[0300] F-containing gas supply time: 1 to 60 minutes, preferably 1 to 30 minutes

[0301] Inert gas supply flow rate (for each gas supply pipe): 0 to 20000 sccm.

[0302] As the F-containing gas, for example, HF gas is preferably used.

[0303] In this step, according to Method 2-A4, the processing conditions for supplying an oxidation gas in the case of forming the SiO film as the base film 304 can be exemplified as follows:

[0304] Processing temperature: 350 to 1200 °C, preferably 400 to 800 °C

[0305] Processing pressure: 1 to 4000 Pa, preferably 1 to 3000 Pa

[0306] Oxidation gas supply flow rate: 1 to 10000 sccm, preferably 100 to 2000 sccm

[0307] Oxidation gas supply time: 0.1 to 60 seconds, preferably 1 to 40 seconds

[0308] Inert gas supply flow rate (for each gas supply pipe): 0 to 20000 sccm.

[0309] As the oxidation gas, the oxidation gas in the above-described first embodiment can be used.

[0310] According to the above respective methods, by performing this step under the above respective processing conditions using the above respective gases, as shown in (b) of Figure 6 of (b), Figure 7 of (b), Figure 8 , Figure 9 of (b), it is possible to selectively (preferably) form the SiO film as the base film 304 on the upper part within the recess 300.

[0311] (Purge)

[0312] After selectively forming the base film 304 on the upper portion within the recess 300, purge the inside of the processing chamber 201 in the same manner as the purge in step A in the first embodiment described above.

[0313] 〔Step B (formation of film formation inhibiting layer)〕

[0314] After step A is completed and the inside of the processing chamber 201 is purged, step B is performed. By supplying a film formation inhibitor to the wafer 200 in step B, as shown in (c) of Figure 6 and (c) of Figure 7 a film formation inhibiting layer 306 is formed on the surface of the base film 304 selectively formed on the upper portion within the recess 300. As a result, the film formation inhibiting layer 306 is formed in a portion corresponding to the upper portion within the recess 300.

[0315] For example, by supplying an F-containing gas as the film formation inhibitor, F radicals can be generated, and an F-capping layer is formed on the entire surface of the base film 304 selectively formed on the upper portion within the recess 300 by the action of the generated F radicals. As a result, the F-capping layer as the film formation inhibiting layer 306 is formed in a portion corresponding to the upper portion within the recess 300 (Method 2-B1).

[0316] In addition, for example, as the film formation inhibitor, by sequentially supplying a Si-containing gas and an F-containing gas, an F-capping layer can be selectively formed on the entire surface of the base film 304 on the upper portion within the recess 300 as the film formation inhibiting layer 306 (Method 2-B2).

[0317] In this case, it is preferable to perform purging of the inside of the processing chamber 201 with an inert gas after supplying the Si-containing gas and before supplying the F-containing gas. In the case of Method 2-B2, by supplying the Si-containing gas, the Si-containing gas can be chemically adsorbed on the entire surface of the base film 304 formed on the upper part in the concave portion 300. Thereafter, by supplying the F-containing gas, the Si-containing gas adsorbed on the entire surface of the base film 304 can react with the F-containing gas to generate F radicals, and by the action of the generated F radicals, an F capping layer is formed as the film formation inhibiting layer 306 on the entire surface of the base film 304. In this case, under the condition that the chemical adsorption of the Si-containing gas on the surface of the base film 304 is saturated, that is, under the condition that the chemical adsorption of the Si-containing gas on the surface of the base film 304 is self-limiting, the Si-containing gas is supplied, so that a chemical adsorption layer of the Si-containing gas can be uniformly formed over the entire surface range of the base film 304. Thereafter, by supplying the F-containing gas, F radicals can be uniformly generated over the entire surface range of the base film 304, and an F capping layer can be uniformly formed as the film formation inhibiting layer 306 over the entire surface range of the base film 304. In this case, as a result, a hydrocarbon capping layer as the film formation inhibiting layer 306 is also formed in the portion corresponding to the upper part in the concave portion 300. It should be noted that, from the viewpoint of the adsorptivity to the surface of the base film 304, an aminosilane gas is preferably used as the Si-containing gas.

[0318] Further, for example, by supplying a hydrocarbon group-containing gas as a film formation inhibitor, the hydrocarbon group-containing gas can be chemically adsorbed on the entire surface of the base film 304 selectively formed on the upper part in the concave portion 300, and a hydrocarbon capping layer can be formed as the film formation inhibiting layer 306 (Method 2-B3).

[0319] In this case, under the condition that the chemical adsorption of the hydrocarbon group-containing gas on the surface of the base film 304 is saturated, that is, under the condition that the chemical adsorption of the hydrocarbon group-containing gas on the surface of the base film 304 is self-limiting, the hydrocarbon group-containing gas is supplied, so that a chemical adsorption layer of the hydrocarbon group-containing gas can be uniformly formed over the entire surface range of the base film 304. In this case, as a result, a hydrocarbon capping layer as the film formation inhibiting layer 306 is formed in the portion corresponding to the upper part in the concave portion 300.

[0320] The methods for supplying the F-containing gas, the hydrocarbon group-containing gas, and the inert gas, and the method for purging the inside of the processing chamber 201 are the same as the corresponding methods in the above-described first embodiment.

[0321] When using Si-containing gas, valve 243d is opened to supply Si-containing gas into gas supply pipe 232d. The flow rate of the Si-containing gas is regulated by MFC241d, supplied into processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, Si-containing gas is supplied to wafer 200. At this time, valves 243e to 243g can also be opened to supply inert gas into processing chamber 201 via nozzles 249a to 249c respectively.

[0322] In this step, according to method 2-B1, the processing conditions when supplying F-containing gas are exemplified as follows:

[0323] Processing temperature: 200 to 600 °C, preferably 350 to 500 °C

[0324] Processing pressure: 1 to 2000 Pa, preferably 1 to 1000 Pa

[0325] Supply flow rate of F-containing gas: 100 to 3000 sccm, preferably 100 to 500 sccm

[0326] Supply time of F-containing gas: 1 to 120 seconds, preferably 1 to 60 seconds

[0327] Supply flow rate of inert gas (for each gas supply pipe): 0 to 20000 sccm.

[0328] As the F-containing gas, the same gas as the F-containing gas in the above first embodiment can be used.

[0329] In this step, according to method 2-B2, the processing conditions when supplying Si-containing gas are exemplified as follows:

[0330] Processing temperature: room temperature (25 °C) to 600 °C, preferably room temperature to 450 °C

[0331] Processing pressure: 1 to 2000 Pa, preferably 1 to 1000 Pa

[0332] Supply flow rate of Si-containing gas: 1 to 2000 sccm, preferably 1 to 500 sccm

[0333] Supply time of Si-containing gas: 1 second to 60 minutes

[0334] Supply flow rate of inert gas (for each gas supply pipe): 0 to 10000 sccm.

[0335] As the Si-containing gas, the raw material gas in the above first embodiment can be used. As the Si-containing gas, for example, aminosilane gas is preferably used.

[0336] In this step, according to Method 2-B2, examples of the processing conditions when supplying the F-containing gas are as follows:

[0337] Processing temperature: room temperature (25°C) to 450°C, preferably 75 to 450°C

[0338] Processing pressure: 1 to 2000 Pa, preferably 1 to 1000 Pa

[0339] F-containing gas supply flow rate: 1 to 2000 sccm, preferably 1 to 500 sccm

[0340] F-containing gas supply time: 1 second to 60 minutes

[0341] Inert gas supply flow rate (for each gas supply pipe): 0 to 10000 sccm.

[0342] As the F-containing gas, the same gas as the F-containing gas in the above-described first embodiment can be used.

[0343] In this step, according to Method 2-B3, examples of the processing conditions when supplying the hydrocarbon group-containing gas are as follows:

[0344] Processing temperature: room temperature (25°C) to 500°C, preferably room temperature to 250°C

[0345] Processing pressure: 5 to 1000 Pa

[0346] Hydrocarbon group-containing gas supply flow rate: 100 to 3000 sccm, preferably 100 to 500 sccm

[0347] Hydrocarbon group-containing gas supply time: 1 second to 120 minutes, preferably 30 seconds to 60 minutes

[0348] Inert gas supply flow rate (for each gas supply pipe): 0 to 20000 sccm.

[0349] As the hydrocarbon group-containing gas, the same gas as the hydrocarbon group-containing gas in the above-described first embodiment can be used.

[0350] According to the above respective methods, by performing this step under the above respective processing conditions using the above respective gases, as shown in (c) of Figure 6 and (c) of Figure 7 it is possible to selectively form the film formation inhibiting layer 306 on the surface of the base film 304 formed on the upper portion within the recess 300.

[0351] (Purge)

[0352] After forming the film formation inhibition layer 306 on the surface of the upper base film 304 selectively formed in the recess 300, the inside of the processing chamber 201 is purged in the same manner as the purge in step B in the first embodiment described above.

[0353] [Step C (selective growth, bottom-up growth)]

[0354] Step C in the present embodiment can be carried out in the same manner as step C in the first embodiment described above. Thus, as Figure 6 shown in (d) to Figure 6 (g) of Figure 7 shown in (d) to Figure 7 (i) of

[0355] For example, a SiN film or a SiON film can be grown bottom-up in the recess 300 as the film 308 from the bottom upward, as shown in (d) to (g) of

[0356] In the first embodiment described above, the film 308 is formed on the entire base film 304 formed in the recess 300. In contrast, in the present embodiment, the film 308 is formed on the surface of the central portion and the lower portion in the recess 300, and on the surface of the base film 304 formed in the recess 300 in the upper portion of the recess 300.

[0357] <Other aspects of the present invention>

[0358] The aspects of the present invention have been specifically described above. However, the present invention is not limited to the above aspects, and various modifications can be made without departing from the gist thereof.

[0359] For example, the base film 304 formed in step A may be a material that has a higher reactivity with the film formation inhibitor than the film formation inhibitor has with the surface within the recess 300 and is capable of forming a film formation inhibiting layer on its surface. For example, as the base film 304, in addition to the above-mentioned SiO film, a SiOCN film, a SiON film, a SiOC film, a SiN film, etc. may also be used. In this case, an effect similar to that of the above-described method can also be obtained. It should be noted that, as described above, as the base film 304, an O-containing film or an oxide film is preferably used, a Si- and O-containing film is more preferably used, and a SiO film is further preferably used.

[0360] In addition, for example, in step C, not only a silicon-based insulating film such as a SiN film or a SiON film may be formed, but also a silicon-based insulating film such as a SiCN, a SiOC film, a SiON film, a SiOCN film, or a SiO film may be formed. In addition, for example, a metal-based oxide film such as an aluminum oxide film (AlO film), a titanium oxide film (TiO film), a hafnium oxide film (HfO film), a zirconium oxide film (ZrO film), a tantalum oxide film (TaO film), a molybdenum oxide film (MoO), or a tungsten oxide film (WO), or a metal-based nitride film such as an aluminum nitride film (AlN film), a titanium nitride film (TiN film), a hafnium nitride film (HfN film), a zirconium nitride film (ZrN film), a tantalum nitride film (TaN film), a molybdenum nitride film (MoN), or a tungsten nitride film (WN) may be formed. In these cases, the above-described pretreatment gas, the above-described film formation inhibitor, the above-described reaction gas, and a source gas containing metal elements such as Al, Ti, Hf, Zr, Ta, Mo, and W can be used, and steps A to C can be performed through treatment steps and treatment conditions similar to those in the above-described first and second embodiments. In these cases, an effect similar to that of the above-described method can also be obtained.

[0361] The manufacturing processes used in each treatment are preferably prepared separately according to the treatment content and stored in the storage device 121c in advance via a telecommunication line or an external storage device 123. And, at the start of each treatment, the CPU 121a preferably appropriately selects an appropriate manufacturing process from among the multiple manufacturing processes stored in the storage device 121c according to the treatment content. Thereby, films having multiple film types, composition ratios, film qualities, and film thicknesses can be formed with good reproducibility using one substrate processing apparatus. In addition, while reducing the burden on the operator and avoiding operation errors, each treatment can be quickly started.

[0362] The above-described process is not limited to newly prepared cases. For example, it can also be prepared by changing the existing process already installed in the substrate processing apparatus. In the case of changing the process, the changed process can also be installed in the substrate processing apparatus via an electrical communication line or a recording medium recording the process. Additionally, the input / output device 122 provided in the existing substrate processing apparatus can be operated to directly change the existing process already installed in the substrate processing apparatus.

[0363] In the above-described manner, an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at a time has been described. The present invention is not limited to the above-described manner. For example, it can also be preferably applied to the case of forming a film using a single-wafer type substrate processing apparatus that processes one or several substrates at a time. Additionally, in the above-described manner, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present invention is not limited to the above-described manner and can also be preferably applied to the case of forming a film using a substrate processing apparatus having a cold-wall type processing furnace.

[0364] In the case of using the above substrate processing apparatus, each process can also be performed with the same processing steps and processing conditions as in the above-described manner, and the same effects as in the above-described manner can be obtained.

[0365] The above-described manners can be used in appropriate combination. The processing steps and processing conditions at this time can be the same as, for example, the processing steps and processing conditions of the above-described manner.

[0366] It should be noted that the respective processing conditions in each step in the above-described first embodiment and second embodiment merely show an example, and can be appropriately adjusted corresponding to the depth of recesses such as grooves and holes provided on the surface of the substrate.

Claims

1. A substrate processing method, comprising the following steps: (a) A step of supplying a pretreatment gas to a substrate having recesses on its surface, thereby forming a base film at least on the upper part within the recesses, wherein the reactivity of the base film with a film formation inhibitor is higher than the reactivity of the film formation inhibitor with the surface within the recesses; (b) A step of forming a film formation inhibiting layer on a portion corresponding to the upper part within the recesses of the surface of the base film formed at least on the upper part within the recesses by supplying the film formation inhibitor to the substrate; and (c) A step of growing a film made of a material different from that of the base film starting from a portion within the recesses where the film formation inhibiting layer is not formed by supplying a film formation gas to the substrate.

2. The substrate processing method according to claim 1, wherein in (a), an oxygen-containing film is formed as the base film.

3. The substrate processing method according to claim 1, wherein in (a), a silicon- and oxygen-containing film is formed as the base film.

4. The substrate processing method according to claim 1, wherein in (a), a silicon oxide film is formed as the base film.

5. The substrate processing method according to claim 1, wherein in (a), the base film is selectively formed on the upper part within the recesses.

6. The substrate processing method according to claim 5, wherein in (a), a source gas is supplied as the pretreatment gas under conditions where a gas-phase reaction predominantly occurs, thereby selectively depositing the base film on the upper part within the recesses.

7. The substrate processing method according to claim 5, wherein in (a), the source gas and the modifying gas are alternately supplied as the pretreatment gas under conditions where at least one of the source gas and the modifying gas is consumed and deactivated at least in part on the upper part within the recesses, thereby selectively depositing the base film on the upper part within the recesses.

8. The substrate processing method according to claim 5, wherein in (a), the pretreatment gas is supplied under conditions where the step coverage deteriorates, and after the base film is deposited within the recesses, an etching gas is supplied under conditions where the base film can be etched conformally, thereby leaving the base film on the upper part within the recesses and exposing the surface of the portion other than the upper part within the recesses.

9. The substrate processing method according to claim 5, wherein in (a), the modifying gas is supplied as the pretreatment gas under conditions where the modifying gas is consumed and deactivated at least in part on the upper part within the recesses, thereby selectively modifying the surface of the upper part within the recesses and selectively forming the base film on the upper part within the recesses.

10. The substrate processing method according to claim 1, wherein in (b), a fluorine-containing gas is supplied as the film formation inhibitor, and a fluorine-capped layer is formed as the film formation inhibiting layer.

11. The substrate processing method according to claim 1, wherein in (b), a hydrocarbon group-containing gas is supplied as the film formation inhibitor, and a hydrocarbon group-capped layer is formed as the film formation inhibiting layer.

12. The substrate processing method according to claim 1, wherein, in (a), the base film is formed throughout the recess.

13. The substrate processing method according to claim 12, wherein, in (a), the base film is deposited in the recess by alternately supplying a source gas and a modifying gas as the pretreatment gas, or the surface in the recess is surface-modified by supplying the modifying gas as the pretreatment gas to form the base film in the recess.

14. The substrate processing method according to claim 12, wherein, in (b), the film formation inhibiting layer is selectively formed on a portion of the surface of the base film formed in the recess corresponding to the upper part in the recess.

15. The substrate processing method according to claim 14, wherein, in (b), the film formation inhibitor is supplied under at least one of the conditions of consumption and inactivation of the film formation inhibitor in the upper part of the recess.

16. The substrate processing method according to claim 14, wherein, in (b), a fluorine-capped layer is formed as the film formation inhibiting layer by supplying a fluorine-containing gas as the film formation inhibitor.

17. The substrate processing method according to claim 14, wherein, in (b), a fluorine-capped layer is formed as the film formation inhibiting layer by supplying the fluorine-containing gas as the film formation inhibitor under the condition of thermal decomposition of the fluorine-containing gas.

18. The substrate processing method according to claim 14, wherein, in (b), a fluorine-capped layer is formed as the film formation inhibiting layer by plasma-exciting and supplying a fluorine-containing gas as the film formation inhibitor.

19. The substrate processing method according to claim 14, wherein, in (b), a fluorine-capped layer is formed as the film formation inhibiting layer by supplying a fluorine-containing gas and an additive gas that reacts with the fluorine-containing gas as the film formation inhibitor.

20. The substrate processing method according to claim 14, wherein, in (b), a hydrocarbon-capped layer is formed as the film formation inhibiting layer by supplying a hydrocarbon group-containing gas as the film formation inhibitor.

21. The substrate processing method according to claim 1, wherein, in (b), the following film formation inhibiting layer is formed: in (c), before the film grows to the upper part in the recess, the film formation inhibiting layer is removed and / or inactivated by the action of the film formation gas.

22. A method for manufacturing a semiconductor device, comprising the following steps: (a) A step of forming a base film at least in the upper part of the recess by supplying a pretreatment gas to a substrate having a recess on its surface, the base film having a higher reactivity with the film formation inhibitor than the reactivity of the film formation inhibitor with the surface in the recess; (b) A step of forming a film formation inhibiting layer on a portion of the surface of the base film formed at least in the upper part of the recess corresponding to the upper part in the recess by supplying the film formation inhibitor to the substrate; and (c) A step of growing a film made of a material different from that of the base film starting from a portion in the recess where the film formation inhibiting layer is not formed by supplying a film formation gas to the substrate.

23. A substrate processing apparatus comprising: A pre-treatment gas supply system that supplies a pre-treatment gas to a substrate; A film formation inhibitor supply system that supplies a film formation inhibitor to the substrate; A film formation gas supply system that supplies a film formation gas to the substrate; and A control unit configured to be able to control the pre-treatment gas supply system, the film formation inhibitor supply system, and the film formation gas supply system to perform the following processes: (a) A process of supplying the pre-treatment gas to a substrate having recesses on its surface to form a base film at least in the upper part of the recesses, the base film having a higher reactivity with the film formation inhibitor than the surface of the recesses with the film formation inhibitor; (b) A process of forming a film formation inhibiting layer on a portion corresponding to the upper part of the recesses in the surface of the base film formed at least in the upper part of the recesses by supplying the film formation inhibitor to the substrate; and (c) A process of growing a film made of a material different from that of the base film starting from a portion in the recess where the film formation inhibiting layer is not formed by supplying the film formation gas to the substrate.

24. A computer-readable recording medium that records a program for causing a computer to cause a substrate processing apparatus to execute the following steps: (a) A step of supplying a pre-treatment gas to a substrate having recesses on its surface to form a base film at least in the upper part of the recesses, the base film having a higher reactivity with a film formation inhibitor than the surface of the recesses with the film formation inhibitor; (b) A step of forming a film formation inhibiting layer on a portion corresponding to the upper part of the recesses in the surface of the base film formed at least in the upper part of the recesses by supplying the film formation inhibitor to the substrate; and (c) A step of growing a film made of a material different from that of the base film starting from a portion in the recess where the film formation inhibiting layer is not formed by supplying a film formation gas to the substrate.

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