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

Abstract

To provide a technique capable of improving the quality of a film formed on a substrate.SOLUTION: A substrate processing method includes the steps of: (a) supplying a first gas containing a group 14 element to a substrate having a recess; (b) supplying a second gas containing a group 15 or 13 element to the substrate; (c) forming a first film containing the group 14 element in the recess by performing (a) and (b) with the second gas as a first concentration and stopping deposition before filling the inside of the recess fully with the first film; and (d) performing (b) with the second gas as a second concentration and subjecting the substrate to heat treatment after (c).SELECTED DRAWING: Figure 4

Description

Technical Field

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

Background Art

[0002] As one step of a semiconductor device manufacturing process, a process of forming a film on a substrate may be performed (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present disclosure provides a technology capable of improving the quality of a film formed on a substrate.

Means for Solving the Problems

[0005] According to one aspect of the present disclosure, (a) a step of supplying a first gas containing a Group 14 element to a substrate having a concave portion; (b) a step of supplying a second gas containing a Group 15 or Group 13 element to the substrate; (c) a step of forming a first film containing the Group 14 element in the concave portion by performing (a) and (b) with the second gas at a first concentration, and stopping film formation before filling the inside of the concave portion with the first film; (d) after (c), performing (b) with the second gas at a second concentration and heat-treating the substrate. A technology having the above is provided.

Effects of the Invention

[0006] According to the present disclosure, it is possible to improve the quality of a film formed on a substrate.

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Mode for Carrying Out the Invention

[0008] <The First Aspect of the Present Disclosure> Hereinafter, the first aspect of the present disclosure will be mainly described with reference to FIGS. 1 to 4 and FIGS. 5(a) to 5(d). It should be noted that the drawings used in the following description are all schematic, and the dimensional relationships and ratios of the respective elements shown in the drawings do not necessarily match the actual ones. Also, the dimensional relationships and ratios of the respective elements do not necessarily match among the plurality of drawings.

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

[0010] 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 (SiO2) or silicon carbide (SiC), and is formed in a cylindrical shape with the upper end closed and the lower end open. 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 the upper and lower ends open. The upper end portion of the manifold 209 is engaged with the lower end portion of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a as a seal 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. Mainly, the reaction tube 203 and the manifold 209 constitute a processing container (reaction container). A processing chamber 201 is formed in the cylindrical hollow portion of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed in this processing chamber 201.

[0011] Inside the processing chamber 201, nozzles 249a to 249e as the first to fifth supply units are respectively provided so as to penetrate the side wall of the manifold 209. Gas supply pipes 232a to 232e are respectively connected to the nozzles 249a to 249e. The nozzles 249a to 249e are different nozzles, and each of the nozzles 249b and 249d is provided adjacent to the nozzle 249c. Each of the nozzles 249a and 249e is provided adjacent to the side opposite to the side adjacent to the nozzles 249b and 249d and the 249c.

[0012] In the gas supply pipes 232a to 232e, mass flow controllers (MFCs) 241a to 241e which are flow rate controllers (flow rate control units) and valves 243a to 243e which are on-off valves are respectively provided in order from the upstream side of the gas flow. On the downstream side of the valves 243a to 243e of the gas supply pipes 232a to 232e, gas supply pipes 232f to 232j are respectively connected. In the gas supply pipes 232f to 232j, MFCs 241f to 241j and valves 243f to 243j are respectively provided in order from the upstream side of the gas flow. The gas supply pipes 232a to 232e are made of a metal material such as SUS, for example.

[0013] As shown in FIG. 2, the nozzles 249a to 249e are provided in an annular space between the inner wall of the reaction tube 203 and the wafer 200, along the upper part from the lower part of the inner wall of the reaction tube 203, so as to rise upward in the arrangement direction of the wafers 200 in a plan view. That is, the nozzles 249a to 249e are respectively provided along the wafer arrangement area in an area that horizontally surrounds the wafer arrangement area on the side of the wafer arrangement area where the wafers 200 are arranged. In a plan view, the nozzle 249c is arranged so as to face the exhaust port 231a (described later) in a straight line across the center of the wafer 200 carried into the processing chamber 201. The nozzles 249b and 249d are arranged so as to sandwich the straight line L passing through the centers of the nozzle 249c and the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer peripheral portion of the wafer 200). Further, each of the nozzles 249a and 249e is arranged so as to sandwich the straight line L from both sides along the inner wall of the reaction tube 203 on the side opposite to the side adjacent to the nozzle 249c of the nozzles 249b and 249d. The straight line L is also a straight line passing through the centers of the nozzle 249c and the wafer 200. That is, it can also be said that the nozzle 249d is provided on the side opposite to the nozzle 249b across the straight line L. Further, it can also be said that the nozzle 249e is provided on the side opposite to the nozzle 249a across the straight line L. The nozzles 249b and 249d are arranged symmetrically with respect to the straight line L as the axis of symmetry. Further, the nozzles 249a and 249e are arranged symmetrically with respect to the straight line L as the axis of symmetry. Gas supply holes 250a to 250e for supplying gas are respectively provided on the side surfaces of the nozzles 249a to 249e. The gas supply holes 250a to 250e are each opened so as to face (opposite) the exhaust port 231a in a plan view, and it is possible to supply gas toward the wafer 200. A plurality of gas supply holes 250a to 250e are provided from the lower part to the upper part of the reaction tube 203.

[0014] From the gas supply pipe 232a, a first gas containing a Group 14 element or a third gas containing a Group 14 element is supplied into the processing chamber 201 through the MFC 241a, the valve 243a, and the nozzle 249a.

[0015] From the gas supply pipe 232b, a second gas containing a Group 15 or Group 13 element is supplied into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.

[0016] From the gas supply pipe 232c, a hydrogen (H)-containing gas is supplied into the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c.

[0017] From the gas supply pipe 232d, a fourth gas containing a Group 14 element is supplied into the processing chamber 201 via the MFC 241d, the valve 243d, and the nozzle 249d.

[0018] From the gas supply pipe 232e, a fourth gas containing a Group 14 element is supplied into the processing chamber 201 via the MFC 241e, the valve 243e, and the nozzle 249e.

[0019] From the gas supply pipes 232f to 232j, an inert gas is supplied into the processing chamber 201 via the MFCs 241f to 241j, the valves 243f to 243j, the gas supply pipes 232a to 232e, and the nozzles 249a to 249e, respectively. The inert gas acts as a purge gas, a carrier gas, a dilution gas, or the like.

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

[0021] Primarily, the first gas supply system or the third gas supply system is constituted by the gas supply pipe 232a, MFC 241a, and valve 243a. Primarily, the second gas supply system is constituted by the gas supply pipe 232b, MFC 241b, and valve 243b. Further, primarily, the H-containing gas supply system is constituted by the gas supply pipe 232c, MFC 241c, and valve 243c. Further, primarily, the fourth gas supply system is constituted by the gas supply pipes 232d, 232e, MFCs 241d, 241e, and valves 243d, 243e. Further, primarily, the inert gas supply system is constituted by the gas supply pipes 232f to 232j, MFCs 241f to 241j, and valves 243f to 243j. Note that the gas supply pipe 232f, MFC 241f, and valve 243f may be considered as included in the first gas supply system or the third gas supply system. The gas supply pipe 232g, MFC 241g, and valve 243g may be considered as included in the second gas supply system. The gas supply pipe 232h, MFC 241h, and valve 243h may be considered as included in the H-containing gas supply system. The gas supply pipes 232i, 232j, MFCs 241i, 241j, and valves 243i, 243j may be considered as included in the fourth gas supply system.

[0022] Among the various supply systems described above, any one or all of the supply systems may be configured as an integrated supply system 248 in which valves 243a to 243j, MFCs 241a to 241j, etc. are integrated. The integrated supply system 248 is connected to each of the gas supply pipes 232a to 232j, and the supply operation of various gases into the gas supply pipes 232a to 232j, that is, the opening and closing operations of the valves 243a to 243j and the flow rate adjustment operations by the MFCs 241a to 241j, etc. are configured to be controlled by a controller 121 described later. The integrated supply system 248 is configured as an integrated unit of an integral type or a split type, and can be attached and detached in units of the integrated unit to the gas supply pipes 232a to 232j, etc., and maintenance, replacement, addition, etc. of the integrated supply system 248 can be performed in units of the integrated unit.

[0023] Below the lower sidewall of the reaction tube 203, an exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided. As shown in FIG. 2, the exhaust port 231a is provided at a position facing (opposite to) the nozzles 249a to 249e (gas supply holes 250a to 250e) with the wafer 200 interposed therebetween in a plan view. The exhaust port 231a may be provided along the upper part from the lower part of the sidewall of the reaction tube 203, that is, along the wafer arrangement region. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via 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). The APC valve 244 can perform vacuum exhaust and stop of vacuum exhaust in the processing chamber 201 by opening and closing the valve in a state where the vacuum pump 246 is operated. Further, in a state where the vacuum pump 246 is operated, 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. Mainly, the exhaust system is constituted by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may be considered to be included in the exhaust system.

[0024] Below the manifold 209, a seal cap 219 is provided as a furnace port lid body that can airtightly close the lower end opening of the manifold 209. The seal cap 219 is made of a metal material such as SUS, for example, and is formed in a disk shape. On the upper surface of the seal cap 219, an O-ring 220b is provided as a seal member that abuts against the lower end of the manifold 209. Below the seal cap 219, a rotation mechanism 267 for rotating the boat 217 described later is installed. The rotation shaft 255 of the rotation mechanism 267 is made of a metal material such as SUS, for example, penetrates the seal cap 219, and is connected to the boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217. The seal cap 219 is configured to be vertically moved up and down by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers the wafer 200 into and out of the processing chamber 201 by moving the seal cap 219 up and down. The transfer device functions as a providing device that provides the wafer 200 into the processing chamber 201.

[0025] Below the manifold 209, a shutter 219s is provided as a furnace port lid body that can airtightly close the lower end opening of the manifold 209 in a state where the seal cap 219 is lowered and the boat 217 is carried out from the inside of the processing chamber 201. The shutter 219s is made of a metal material such as SUS, for example, and is formed in a disk shape. On the upper surface of the shutter 219s, an O-ring 220c is provided as a seal member that abuts against the lower end of the manifold 209. The opening and closing operation (lifting operation, rotation operation, etc.) of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

[0026] The boat 217 as a substrate support is configured to support a plurality of wafers 200, for example, 25 to 200 wafers 200, in a horizontal posture and vertically aligned in a multi-stage manner with their centers aligned with each other, that is, arranged in a direction perpendicular to the surface of the wafers 200 with intervals. The boat 217 is made of a heat-resistant material such as quartz or SiC, for example. A heat insulating plate 218 made of a heat-resistant material such as quartz or SiC is supported in multiple stages below the boat 217.

[0027] A temperature sensor 263 as a temperature detector is installed in the reaction tube 203. By adjusting the energization of the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature 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.

[0028] As shown in FIG. 3, the controller 121, which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, the storage device 121c, and the I / O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122 configured as a touch panel or the like, for example, is connected to the controller 121. In addition, an external storage device 123 can be connected to the controller 121.

[0029] The storage device 121c is composed of, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), or the like. In the storage device 121c, a control program for controlling the operation of the substrate processing apparatus, a process recipe, etc. describing the procedures and conditions of substrate processing described later, are recorded and stored in a readable manner. The process recipe is a combination of the respective procedures in the substrate processing described later, which can be executed by the controller 121 on the substrate processing apparatus to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the control program, etc. are collectively referred to simply as a program. Also, the process recipe is simply referred to as a recipe. When the term "program" is used in this specification, it may include only the recipe alone, only the control program alone, or both of them. The RAM 121b is configured as a memory area (work area) that temporarily holds programs, data, etc. read by the CPU 121a.

[0030] The I / O port 121d is connected to the above-described MFCs 241a to 241j, valves 243a to 243j, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, shutter opening / closing mechanism 115s, etc.

[0031] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to be able to read a recipe 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 controls operations such as the flow rate adjustment operation of various substances (various gases) by the MFCs 241a to 241g, the opening and closing operations of the valves 243a to 243g, the opening and closing operation of the APC valve 244, the pressure adjustment operation by the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting operation of the boat 217 by the boat elevator 115, and the opening and closing operation of the shutter 219s by the shutter opening / closing mechanism 115s, so as to conform to the content of the read recipe.

[0032] The controller 121 can be configured by installing the above-described program recorded and stored in the external storage device 123 on a computer. The external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, a semiconductor memory such as a USB memory or an SSD, and the like. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media. When the term "recording medium" is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both of them. Note that the program may be provided to the computer without using the external storage device 123, but by using a communication means such as the Internet or a dedicated line.

[0033] (2) Substrate processing step An example of a processing sequence for forming a film on a wafer 200 as a substrate, as one step of a semiconductor device manufacturing process, will be mainly described with reference to FIGS. 4, 5(a) to 5(d) using the above-described substrate processing apparatus. In the following description, the operations of each part constituting the substrate processing apparatus are controlled by the controller 121.

[0034] As the wafer 200, for example, a Si substrate made of single crystal silicon (Si) or a substrate having a single crystal Si film formed on its surface can be used. As shown in FIG. 5(a), a recess is provided on the surface of the wafer 200. The bottom of the recess is made of, for example, single crystal Si, and the side and upper portions of the recess are made of an insulating film 200a such as a silicon nitride film (SiN film). The surface of the wafer 200 is in a state where the single crystal Si and the insulating film 200a are respectively exposed.

[0035] In the processing sequence of this aspect, (a) A step of supplying a first gas containing a Group 14 element to the wafer 200 having a recess, (b) A step of supplying a second gas containing a Group 15 or Group 13 element to the wafer 200, (c) With the second gas at a first concentration, by performing (a) and (b), a first film containing a Group 14 element is formed in the recess, and a step of stopping film formation before filling the inside of the recess with the first film (film formation step), (d) After (c), performing (b) with the second gas at a second concentration and a step of heat-treating the wafer 200 (heat treatment step) are performed.

[0036] Hereinafter, as an example, the case where the first gas and the second gas are simultaneously supplied in the film formation step will be described.

[0037] In this specification, the above-described processing sequence may be shown as follows for convenience. The same notation will be used in the description of the following modification examples and other aspects.

[0038] First gas + Second gas → Second gas + Heat treatment

[0039] Also, as shown in FIG. 4, the processing sequence of this aspect further includes a pre-film formation seed layer formation step of forming a seed layer on the wafer 200 by supplying a fourth gas containing a Group 14 element to the wafer 200 before performing the film formation step.

[0040] In this specification, for convenience, the above-described processing sequence may be shown as follows. The same notation will be used in the descriptions of the following modified examples and other aspects as well.

[0041] Fourth gas → First gas + Second gas → Second gas + Heat treatment

[0042] The term "wafer" as used in this specification may mean the wafer itself or a laminate of the wafer and a predetermined layer or film formed on its surface. The term "surface of the wafer" as used in this specification may mean the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. When it is described in this specification that "a predetermined layer is formed on the wafer", it may mean directly forming a predetermined layer on the surface of the wafer itself or forming a predetermined layer on a layer or the like formed on the wafer. When the term "substrate" is used in this specification, it has the same meaning as when the term "wafer" is used.

[0043] The term "layer" as used in this specification includes at least either a continuous layer or a discontinuous layer.

[0044] (Wafer charge and boat load) When a plurality of wafers 200 are loaded (wafer charge) into the boat 217, the shutter 219s is moved by the shutter opening / closing mechanism 115s, and the lower end opening of the manifold 209 is opened (shutter open). Then, as shown in FIG. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and carried into (boat load) the processing chamber 201. In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b. In this way, the wafers 200 are prepared inside the processing chamber 201.

[0045] (Pressure adjustment and temperature adjustment) After the boat load is completed, the inside of the processing chamber 201, that is, the space where the wafer 200 is located, is evacuated (depressurized and evacuated) by the vacuum pump 246 so as to reach a desired pressure (degree of vacuum). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. Also, the wafer 200 inside the processing chamber 201 is heated by the heater 207 so as to reach a desired processing temperature. At this time, the energization of the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. Also, the rotation of the wafer 200 by the rotation mechanism 267 is started. The evacuation inside the processing chamber 201, the heating of the wafer 200, and the rotation are all continuously performed until at least the processing of the wafer 200 is completed.

[0046] (Seed layer formation step before film formation) Thereafter, a fourth gas containing a Group 14 element is supplied to the wafer 200. This step is performed, for example, using two types of gases among the fourth gases containing Si as the Group 14 element. Hereinafter, an example of forming the seed layer 301 by performing a cycle including a halosilane-based gas supply step and a silane-based gas supply step, which includes one of the two types of gases as a halosilane-based gas containing Si and halogen and the other as a silane-based gas containing Si, a predetermined number of times (n times, n is an integer of 1 or more) will be described. In this specification, the formation sequence of the seed layer 301 may be shown as follows for convenience.

[0047] (Halosilane-based gas → Silane-based gas) × n

[0048] [Halosilane-based gas supply step] In this step, a halosilane-based gas is supplied to the wafer 200.

[0049] Specifically, open valve 243d and flow the halosilane gas into gas supply pipe 232d. The flow rate of the halosilane gas is adjusted by MFC241d, and it is supplied into processing chamber 201 through gas supply pipe 232d and nozzle 249d, and exhausted from exhaust port 231a. At this time, the halosilane gas is supplied to wafer 200 from the side of wafer 200 (halosilane gas supply). At this time, valves 243f to 243j may be opened to supply an inert gas into processing chamber 201 through each of nozzles 249a to 249e.

[0050] By supplying the halosilane gas to wafer 200 under the processing conditions described below, the treatment action (etching action) of the halosilane gas can remove the native oxide film, impurities, etc. from the surface of wafer 200, and clean this surface.

[0051] The processing conditions in this step are as follows: Processing temperature: 250 to 450 °C, preferably 300 to 400 °C Processing pressure: 400 to 1000 Pa Halosilane gas supply flow rate: 0.1 to 1 slm Inert gas supply flow rate (per gas supply pipe): 0 to 5 slm Each gas supply time: 0.5 to 10 minutes are exemplified.

[0052] Note that the notation of a numerical range such as "250 to 450 °C" in this specification means that the lower limit value and the upper limit value are included in that range. Therefore, for example, "250 to 450 °C" means "250 °C or higher and 450 °C or lower". The same applies to other numerical ranges. Also, the processing temperature in this specification means the temperature of wafer 200 or the temperature in processing chamber 201, and the processing pressure means the pressure in processing chamber 201. Also, the processing time means the time for which the processing is continued. Also, when 0 slm is included in the supply flow rate, 0 slm means the case where that substance (gas) is not supplied. These are the same in the following description.

[0053] After the surface of the wafer 200 is cleaned, the valve 243d is closed and the supply of the halosilane gas into the processing chamber 201 is stopped. Then, the inside of the processing chamber 201 is evacuated to remove gaseous substances and the like remaining in the processing chamber 201 from the processing chamber 201. At this time, the valves 243f to 243j are opened and an inert gas is supplied into the processing chamber 201 through the nozzles 249a to 249e. The inert gas supplied from the nozzles 249a to 249e acts as a purge gas, whereby the inside of the processing chamber 201 is purged (purge).

[0054] The processing conditions for performing the purge in this step are as follows. Processing temperature: room temperature (25 °C) to 600 °C Processing pressure: 1 to 30 Pa Inert gas supply flow rate (per gas supply pipe): 0.5 to 20 slm Inert gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds are exemplified.

[0055] As the halosilane gas, for example, chlorosilane gases such as dichlorosilane (SiH2Cl2, abbreviation: DCS) gas, monochlorosilane (SiH3Cl, abbreviation: MCS) gas, tetrachlorosilane (SiCl4, abbreviation: STC) gas, trichlorosilane (SiHCl3, abbreviation: TCS) gas, hexachlorodisilane (Si2Cl6, abbreviation: HCDS) gas, octachlorotrisilane (Si3Cl8, abbreviation: OCTS) gas can be used. Further, as the halosilane gas, for example, tetrafluorosilane (SiF4) gas, tetrabromosilane (SiBr4) gas, tetraiodosilane (SiI4) gas and the like can be used. Thus, as the halosilane gas, for example, in addition to chlorosilane gases, halosilane gases such as fluorosilane gases, bromosilane gases, and iodosilane gases can be used. As the halosilane gas, one or more of these can be used.

[0056] As the inert gas, nitrogen (N2) gas, or noble gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas, etc. can be used. As the inert gas, one or more of these can be used. This also applies to each step described later.

[0057] [Silane-based gas supply step] After the halosilane-based gas supply step is completed, a silane-based gas is supplied to the surface of the wafer 200 in the processing chamber 201, that is, the surface of the cleaned wafer 200.

[0058] Specifically, the valve 243e is opened, and the silane-based gas is flowed into the gas supply pipe 232e. The silane-based gas is adjusted in flow rate by the MFC241e, supplied into the processing chamber 201 through the nozzle 249e, and exhausted from the exhaust port 231a. At this time, the silane-based gas is supplied to the wafer 200 from the side of the wafer 200 (silane-based gas supply). At this time, the valves 243f to 243j may be opened to supply an inert gas into the processing chamber 201 through each of the nozzles 249a to 249e.

[0059] By supplying the silane-based gas to the wafer 200 under the processing conditions described later, Si contained in the silane-based gas can be adsorbed on the surface of the wafer 200 to form seeds (nuclei). Under the processing conditions described later, the crystal structure of the nuclei formed on the surface of the wafer 200 varies depending on the surface state where the nuclei are formed. For example, the crystal structure of the seeds formed at the bottom of the concave portion includes at least one of single crystal, polycrystal, and amorphous (non-crystalline), and the crystal structure of the seeds formed on the insulating film 200a is amorphous.

[0060] The processing conditions in this step are as follows: Silane-based gas supply flow rate: 0.05 to 1 slm Each gas supply time: 0.5 to 10 minutes are exemplified. Other processing conditions can be the same as the processing conditions in the halosilane-based gas supply step.

[0061] After a seed is formed on the surface of the wafer 200, the valve 243e is closed, and the supply of the silane-based gas into the processing chamber 201 is stopped. Then, in the same processing procedure and processing conditions as the purge step in the halosilane-based gas supply step, the gas and the like remaining in the processing chamber 201 are removed from the processing chamber 201.

[0062] As the silane-based gas, for example, silane (SiH4, abbreviation: MS) gas, disilane (Si2H6, abbreviation: DS) gas, trisilane (Si3H8) gas, tetrasilane (Si4H 10 ) gas, pentasilane (Si5H 12 ) gas, hexasilane (Si6H 14 ) gas and other silicon hydride gases can be used. As the silane-based gas, one or more of these can be used.

[0063] [Performed a predetermined number of times] By performing the cycle of alternately performing the above-described halosilane-based gas supply step and silane-based gas supply step non-simultaneously, that is, without synchronization, a predetermined number of times (n times, n is an integer of 1 or more), a seed layer 301 in which the above-described seeds are formed at a high density can be formed on the surface of the wafer 200. In particular, by performing the above-described cycle a plurality of times, the seed layer 301 can be uniformly formed on the surface of the concave portion (see FIG. 5(a)). Under the above-described processing conditions, the crystal structure of the seed layer 301 formed at the bottom of the concave portion becomes single crystal or amorphous, and the crystal structure of the seed layer 301 formed on the insulating film 200a becomes amorphous. Note that the surface of the concave portion means either one or both of the surface of the insulating film 200a and the bottom of the concave portion.

[0064] (Film formation step) Thereafter, a first gas containing a Group 14 element and a second gas containing a Group 15 or Group 13 element are supplied to the wafer 200 in the processing chamber 201.

[0065] Specifically, open valves 243a and 243b, and flow the first gas and the second gas into gas supply pipes 232a and 232b, respectively. The first gas and the second gas are each adjusted in flow rate by MFCs 241a and 241b, supplied into the processing chamber 201 through nozzles 249a and 249b, mixed in the processing chamber 201, and exhausted from exhaust port 231a. At this time, the first gas and the second gas are supplied to the wafer 200 from the side of the wafer 200 (first gas + second gas supply). At this time, valves 243f to 243j may be opened to supply an inert gas into the processing chamber 201 through each of nozzles 249a to 249e.

[0066] Under the processing conditions described later, for example, by supplying a first gas containing Si as a Group 14 element and a second gas containing phosphorus (P) as a Group 15 element to the wafer 200, at least the first gas is decomposed in the gas phase, and Si is adsorbed (deposited) on the surface of the wafer 200, that is, on the seed layer 301 formed on the wafer 200, and a first film 302 as a Si film doped with P can be formed. Under the processing conditions described later, the crystal structure of the first film 302 formed on the wafer 200 becomes, for example, amorphous.

[0067] The processing conditions in this step are as follows: Processing temperature: 300 to 500 °C, preferably 350 to 450 °C Processing pressure: 100 to 800 Pa, preferably 400 to 700 Pa First gas supply flow rate: 0.5 to 1 slm Second gas supply flow rate: 0.001 to 2 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm Each gas supply time: 1 to 300 minutes are exemplified.

[0068] The concentration of the second gas in the processing chamber 201 in this step is the first concentration. In this specification, the concentration of the second gas means, for example, the volume (cm 3 ) of the second gas at normal temperature and normal pressure with respect to the volume (cm 3) is referred to as

[0069] As described above, it is preferable that the processing temperature in this step is higher than the processing temperature in the seed layer formation step before film formation.

[0070] After a predetermined time has elapsed, valves 243a and 243b are closed, and the supply of the first gas and the second gas into the processing chamber 201 is stopped respectively. Thereby, film formation can be stopped before the recess provided in the wafer 200 is filled with the first film 302. By stopping film formation before the recess is filled with the first film 302, voids and seams and other gaps will occur in the recess (see Fig. 5(b)). Then, in the same processing procedure and processing conditions as the purge in the seed layer formation step before film formation, the gaseous substances and the like remaining in the processing chamber 201 are removed from the processing chamber 201 (purge).

[0071] As the first gas, for example, silane gas (SiH4, abbreviation: MS), disilane gas (Si2H6, abbreviation: DS), trisilane gas (Si3H8), tetrasilane gas (Si4H 10 ) gas, pentasilane gas (Si5H 12 ) gas, hexasilane gas (Si6H 14 ) gas and other silicon hydride gases containing Si as the fourteenth group element can be used. As the first gas, for example, germane gas (GeH4), digermane gas (Ge2H6), trigermane gas (Ge3H8), tetragermane gas (Ge4H 10 ) gas, pentagermane gas (Ge5H 12 ) gas, hexagermane gas (Ge6H 14 ) gas and other germanium hydride gases containing Ge (germanium) as the fourteenth group element can be used. As the first gas, one or more of these can be used. As the first gas, it is preferable to use any one of, for example, MS gas, DS gas, trisilane gas, germane gas, digermane gas, or trigermane gas among these. Since these react (decompose) relatively easily, the film formation rate can be improved. Also, as the first film 302, a film containing both Si and Ge can be used.

[0072] As the second gas, for example, phosphine (PH3) gas, diphosphine (P2H6) gas, or other phosphine-based gases containing P as a Group 15 element, or phosphorus halide gas such as phosphorus trichloride (PCl3) gas can be used. As the second gas, for example, borane-based gases (also called boron hydride-based gases) such as monoborane (BH3) gas, diborane (B2H6) gas, triborane (B3H8) gas, or boron halide gas such as boron trichloride (BCl3) gas, aluminum chloride (AlCl3) gas, gallium chloride (GaCl3) gas, indium chloride (InCl3) gas, or other halides containing any of boron (B), aluminum (Al), gallium (Ga), or indium (In) as a Group 13 element can be used. As the second gas, one or more of these can be used. This also applies to the temperature increase step and heat treatment step described later.

[0073] (Heat treatment step) Thereafter, by performing heat treatment on the wafer 200, Group 14 elements contained in the first film 302, such as Si, are migrated. Thereby, the inside of the recess can be filled with the first film 302, and voids and seams generated in the film formation step can be eliminated. At this time, in order to promote the migration of Si, it is preferable to reduce the pressure in the processing chamber 201 or supply an H-containing gas into the processing chamber 201.

[0074] However, when heat treatment is performed on the wafer 200, for example, P doped in the first film 302 in the film formation step may diffuse outward from the first film 302. In particular, when the pressure in the processing chamber 201 is reduced or an H-containing gas is supplied into the processing chamber 201 to promote the migration of Si, the outward diffusion of P becomes significant.

[0075] Therefore, in the heat treatment step, for example, a second gas containing P as a Group 15 element is supplied. Thereby, it becomes possible to dope P into the first film 302 and supplement P that diffuses outward from the first film 302.

[0076] The processing procedures and conditions of the heat treatment steps will be described below.

[0077] A second gas, an H-containing gas, is supplied to the wafer 200, and the wafer 200 is heated (heat treated).

[0078] Specifically, valves 243b and 243c are opened, and the second gas and the H-containing gas are allowed to flow into the gas supply pipes 232b and 232c. The second gas and the H-containing gas are each adjusted in flow rate by MFCs 241b and 241c, supplied into the processing chamber 201 through nozzles 249b and 249c, mixed in the processing chamber 201, and exhausted from the exhaust port 231a. At this time, the second gas and the H-containing gas are supplied to the wafer 200 from the side of the wafer 200 (second gas + H-containing gas supply). At this time, valves 243f to 243j may be opened to supply an inert gas into the processing chamber 201 through each of the nozzles 249a to 249e.

[0079] The processing conditions in this step are as follows: Processing temperature: 400 to 700 °C, preferably 450 to 600 °C Processing pressure: 30 to 200 Pa, preferably 50 to 150 Pa Second gas supply flow rate: 0.3 to 0.8 slm H-containing gas supply flow rate: 0.001 to 2 slm Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm Each gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds are exemplified.

[0080] By performing a heat treatment on the wafer 200 under the above processing conditions, for example, Si contained in the first film 302 can be migrated. Note that, for example, the migration of Si occurs in the direction in which the film thickness of the first film 302 is flattened. In this embodiment, as shown in FIG. 5(b), since the first film 302 is formed on the surface of the concave portion, Si moves from the upper side to the bottom side of the concave portion (see the arrow in FIG. 5(c)). In this way, it becomes possible to fill the inside of the concave portion with the first film 302 and eliminate voids and seams (see FIG. 5(d)).

[0081] The concentration of the second gas in the processing chamber 201 in this step is the second concentration. The second concentration is a concentration different from the first concentration, and is preferably lower than the first concentration.

[0082] As described above, it is preferable that the pressure in the processing chamber 201 in this step is lower than the pressure in the processing chamber 201 in the film formation step.

[0083] After filling the inside of the concave portion with the first film 302, close the valves 243b and 243c and stop the supply of the second gas and the H-containing gas into the processing chamber 201. Then, the gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 (purged) by the same processing procedure and processing conditions as in the purge in the pre-film formation seed layer formation step.

[0084] As the H-containing gas, for example, a gas containing H can be used. Specifically, H2 gas, deuterium (D2) gas, activated H gas, etc. can be used. As the H-containing gas, one or more of these can be used.

[0085] (After purge and return to atmospheric pressure) After the heat treatment step is completed, an inert gas as a purge gas is supplied into the processing chamber 201 from each of the nozzles 249a to 249e, 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 (after purge). Then, 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).

[0086] (Boat unloading and wafer discharge) Thereafter, the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafer 200 is carried out (boat unloading) from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the boat 217. After the boat unloading, the shutter 219s is moved, and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). After the processed wafer 200 is carried out to the outside of the reaction tube 203, it is taken out from the boat 217 (wafer discharge).

[0087] (3) Effects of this embodiment According to this embodiment, one or more of the following effects can be obtained.

[0088] (a) By setting the concentration of the second gas in the film formation step to the first concentration and the concentration of the second gas in the heat treatment step to the second concentration, and making these concentrations different, the amount of P doped into the first film 302 can be adjusted.

[0089] As described above, by supplying the second gas in the heat treatment step and doping, for example, P into the first film 302, it is possible to supplement, for example, P that diffuses outward from the first film 302 in the heat treatment step. At this time, by making the first concentration and the second concentration different, the amount of P doped into the first film 302 can be adjusted. Thereby, the quality of the first film 302 can be improved.

[0090] (b) By making the concentration of the second gas (second concentration) in the heat treatment step lower than the concentration of the second gas (first concentration) in the film formation step, in the heat treatment step, the amount of, for example, P diffusing outward from the first film 302 and the amount of, for example, P diffusing from the outside into the first film 302 and being doped in the first film 302 can be made closer to each other.

[0091] As described above, when the wafer 200 is heat-treated, for example, P doped in the first film 302 in the film formation step may diffuse outward from the first film 302. At this time, in particular, the diffusion of, for example, P existing near the surface of the first film 302 to the outside of the first film 302 is promoted, so there is a possibility that non-uniformity in the P concentration in the first film 302 may occur.

[0092] By making the second concentration lower than the first concentration, the amount of P diffusing outward from the first film 302 and the amount of P diffusing from the outside into the first film 302 and being doped in the first film 302 in the heat treatment step can be made closer to each other. Thereby, the doping amount of P from the lower side to the surface side of the first film 302 can be made uniform, that is, the P concentration in the first film 302 can be made uniform. As a result, the quality of the first film 302 can be reliably improved.

[0093] (c) In the heat treatment step, by supplying an H-containing gas to the wafer 200 and adsorbing H on the surface of the first film 302, the migration of, for example, Si contained in the first film 302 can be promoted. Thereby, the embedding by the first film 302 in the concave portion can be promoted, and voids and seams can be easily eliminated. The embedding characteristics by the first film 302 in the concave portion can be improved.

[0094] (d) By making the pressure inside the processing chamber 201 in the heat treatment step lower than the pressure inside the processing chamber 201 in the film formation step, in the heat treatment step, for example, Si contained in the first film 302 can be physically pulled, and the migration of Si can be promoted. Thereby, the embedding of the first film 302 in the concave portion can be promoted, and voids and seams can be easily eliminated. The embedding characteristics of the first film 302 in the concave portion can be improved.

[0095] (e) In the heat treatment step, by supplying an inert gas to the wafer 200 inside the processing chamber 201, for example, P doped in the first film 302 can be suppressed from diffusing outward from the first film 302. Preferably, by setting the pressure inside the processing chamber 201 to an atmosphere that is not under reduced pressure, for example, P doped in the first film 302 can be further suppressed from diffusing outward from the first film 302.

[0096] (f) Before performing the film formation step, by performing a pre-film formation seed layer formation step to form a seed layer 301 on the surface of the concave portion, it becomes possible to form a first film 302 having a uniform thickness over the entire area inside the concave portion, that is, a first film 302 having high step coverage. Also, by making the processing temperature in the film formation step higher than the processing temperature in the pre-film formation seed layer formation step, it becomes possible to form a first film 302 having high step coverage.

[0097] (g) By performing the silane-based gas supply step under the above-described temperature conditions, the thermal decomposition of the silane-based gas is suppressed, and the controllability of the thickness of the seed layer 301 formed on the wafer 200 is enhanced. For example, the thickness of the seed layer 301 can be made less than the thickness of one atomic layer.

[0098] The above-described effects can be similarly obtained even when a predetermined substance (gaseous substance, liquid substance) is arbitrarily selected and used from the above-described various first gases, various second gases, various fourth gases, and various inert gases.

[0099] <Second Aspect of the Present Disclosure> Hereinafter, as one step in the manufacturing process of a semiconductor device in the second aspect of the present disclosure, an example of a processing sequence for forming a film on a wafer 200 as a substrate will be mainly described with reference to FIGS. 6, 7(a) to 7(e). Note that all the drawings used in the following description are schematic, and the dimensional relationships and ratios of the respective elements shown in the drawings do not necessarily match the actual ones. Also, the dimensional relationships and ratios of the respective elements do not necessarily match among the plurality of drawings. In the following description, the operations of each part constituting the substrate processing apparatus are controlled by the controller 121.

[0100] For example, as shown in FIG. 7(a), recesses are provided on the surface of the wafer 200. In this aspect, as an example, the bottom of the recess is made of, for example, single-crystalline Si, and the side and upper portions of the recess are made of an insulating film 200a such as an SiN film, as in the above-described aspect. The surface of the wafer 200 is in a state where the single-crystalline Si and the insulating film 200a are respectively exposed.

[0101] In the processing sequence in this aspect, (A) A step of supplying a first gas containing a Group 14 element to the wafer 200 having recesses, (B) A step of supplying a second gas containing a Group 15 or Group 13 element to the wafer 200, (C) By performing (A) and (B), a first film 302 containing a Group 14 element is formed in the recesses, and a step of stopping film formation (film formation step) before filling the inside of the recesses with the first film 302, (D) After (C), a step of supplying a third gas containing a Group 14 element to the wafer 200 to form a second film 303 containing a Group 14 element on the surface of the recesses (post-film formation seeding step), (E) After (D), a step of heat-treating the wafer 200 (heat treatment step) are performed.

[0102] Hereinafter, as an example, in the film formation step, the case where the first gas and the second gas are simultaneously supplied will be described.

[0103] In this specification, for convenience, the above-described processing sequence may be shown as follows. The same notation will be used in the description of the following modification examples and other aspects.

[0104] First gas + Second gas → Third gas → Heat treatment

[0105] Also, as shown in FIG. 6, the processing sequence of this aspect may further include a pre-film formation seed layer formation step of forming a seed layer 301 on the wafer 200 by supplying a fourth gas containing a Group 14 element to the wafer 200 before performing the film formation step.

[0106] In this specification, for convenience, the above-described processing sequence may be shown as follows. The same notation will be used in the description of the following modification examples and other aspects.

[0107] Fourth gas → First gas + Second gas → Third gas → Heat treatment

[0108] In this aspect, an example of sequentially performing the pre-film formation seed layer formation step, the film formation step, the post-film seeding step, and the heat treatment step will be described. The first gas, the second gas, the fourth gas, and the inert gas used in this aspect can be the same first gas, second gas, fourth gas, and inert gas as those in the above-described aspect.

[0109] The processing procedures for wafer charge, boat load, pressure adjustment, temperature adjustment, after purge, and atmospheric pressure recovery in this aspect can be the same as those processing procedures in the above-described aspect, respectively. Also, the processing procedures and processing conditions in the pre-film formation seed layer formation step and the film formation step of this aspect can be the same as the processing procedures and processing conditions in the pre-film formation seed layer formation step and the film formation step of the above-described aspect.

[0110] However, the concentration of the second gas in the film formation step of this embodiment is not particularly limited to the first concentration exemplified as the concentration of the second gas in the film formation step of the above-described embodiment.

[0111] In this embodiment, by performing the seed layer formation step before film formation, a seed layer 301 is formed on the surface of the recess (see Fig. 7(a)), and then by performing the film formation step, a first film 302 is formed on the surface of the recess (see Fig. 7(b)). In the film formation step, similar to the above-described embodiment, by stopping film formation before filling the inside of the recess with the first film 302, voids and gaps such as seams are generated in the recess.

[0112] Hereinafter, the processing procedures and processing conditions in the post-film formation seeding step and the heat treatment step will be described.

[0113] (Post-film formation seeding step) In this step, a third gas containing a Group 14 element and a second gas are supplied to the wafer 200 in the processing chamber 201.

[0114] Specifically, valves 243a and 243b are opened, and the third gas and the second gas are respectively flowed into the gas supply pipes 232a and 232b. The third gas and the second gas are respectively adjusted in flow rate by MFCs 241a and 241b, supplied into the processing chamber 201 through nozzles 249a and 249b, mixed in the processing chamber 201, and exhausted from the exhaust port 231a. At this time, the third gas and the second gas are supplied to the wafer 200 from the side of the wafer 200 (third gas + second gas supply). At this time, valves 243f to 243j may be opened to supply an inert gas into the processing chamber 201 through each of the nozzles 249a to 249e.

[0115] The processing conditions in this step are as follows: Processing temperature: 350 to 700 °C, preferably 400 to 650 °C Processing pressure: 400 to 1000 Pa Third gas supply flow rate: 0.1 to 1 slm Second gas supply flow rate: 0.001 to 2 slm Inert gas supply flow rate (per gas supply pipe): 0 - 20 slm Each gas supply time: 1 - 100 minutes is exemplified.

[0116] Under the above-described processing conditions, for the wafer 200, for example, by supplying a third gas containing Si as a Group 14 element, Si contained in the third gas can be adsorbed onto the first film 302, and a seed (nucleus) for the second film 303 can be formed. As shown in FIG. 7(c), the second film 303 is formed discontinuously, for example, in a crystal nucleus shape, on the first film 302 within the recess. Under the above-described processing conditions, the crystal structure of the formed second film 303 is in a state including at least either single crystal or polycrystal. Note that a discontinuous film is also referred to as an island-like film, a film with sparsely formed crystal nuclei, or a granular film.

[0117] Under the above-described processing conditions, for example, by controlling at least any one of the supply flow rate of the third gas, the supply time of the third gas, and the processing pressure, for example, the particle size and density of the second film 303 in the form of crystal nuclei can be controlled. For example, by increasing at least any one of the supply flow rate of the third gas, the supply time of the third gas, and the processing pressure, the particle size of the second film 303 on the first film 302 can be increased, or the density of the second film 303 can be increased.

[0118] As described above, it is preferable that the processing temperature in this step is higher than the processing temperature in the pre-film seed layer formation step and the film formation step described above.

[0119] After forming the second film 303 on the first film 302, the valves 243a and 243b are closed, and the supply of the third gas and the second gas into the processing chamber 201 is stopped respectively. Then, in the same processing procedure and under the same processing conditions as the purge in the pre-film seed layer formation step in the above-described manner, gaseous substances and the like remaining in the processing chamber 201 are removed from the processing chamber 201 (purge).

[0120] As the third gas, for example, hydrogen compounds such as DCS gas, MS gas, DS gas, trisilane gas, tetrasilane gas, pentasilane gas, hexasilane gas, germane gas, digermane gas, trigermane gas, tetragermane gas, pentagermane gas, hexagermane gas, etc., which contain Si or Ge as a Group 14 element, can be used. As the third gas, one or more of these can be used. Since these gases decompose relatively easily, they can form crystal nucleus-like seeds. Further, among these gases, it is preferable to use gases that do not contain halogen, that is, gases other than DCS gas. Since these gases decompose more easily, they can surely form crystal nucleus-like seeds. Also, as the third gas, it is preferable to use a gas (compound) different from the above-described fourth gas. The pre-film seed layer formation step and the post-film seeding step are common in that a seed is formed on the wafer 200. However, in the post-film seeding step, a discontinuous film is formed, while in the pre-film seed layer formation step, a continuous film (uniform film) is formed, so the films formed are different. By using different gases, it is possible to easily form these different films.

[0121] (Heat treatment step) Thereafter, the wafer 200 is heated (heat-treated).

[0122] The processing conditions in this step are as follows: Processing temperature: 400 to 750 °C, preferably 450 to 700 °C Processing pressure: 30 to 200 Pa, preferably 50 to 150 Pa Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm Inert gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds are exemplified.

[0123] By performing a heat treatment on the wafer 200 under the above-described processing conditions, the first film 302 can be crystallized, and accordingly, the particle size of the second film 303 can be increased. In this embodiment, for convenience, the crystallized first film 302 and the second film 303 whose particle size has increased with the crystallization of the first film 302 are combined and referred to as the third film 304 (see FIG. 7(d)). By performing this step, the inside of the recess can be filled with the third film 304, and voids and seams can be eliminated (see FIG. 7(e)).

[0124] After filling the inside of the recess with the third film 304, stop the output of the heater 207. Then, by the same processing procedure and processing conditions as the purge in the seed layer formation step before film formation in the above-described embodiment, the gaseous substances and the like remaining in the processing chamber 201 are removed from the processing chamber 201 (purge).

[0125] According to this embodiment, in addition to at least some of the effects described in the above-described embodiment, one or more of the following effects can be obtained.

[0126] In the post-film formation seeding step, by supplying, for example, a third gas containing Si as a Group 14 element to the wafer 200, Si contained in the third gas can be adsorbed on the first film 302, and a seed (second film 303) can be formed on the first film 302 in the recess. Further, in the heat treatment step, by heating the wafer 200, the first film 302 can be crystallized, and accordingly, the particle size of the second film 303 can be increased. As a result, the inside of the recess can be filled with the third film 304, and voids and seams can be eliminated. In this way, the embedding characteristics of the third film 304 in the recess can be improved, and the quality of the third film 304 can be improved.

[0127] In the post-deposition seeding step, the surface roughness of the first film 302 can be controlled by forming the second film 303 discontinuously, for example, in the form of crystal nuclei, on the first film 302. Specifically, for example, in the post-deposition seeding step, by adjusting the supply flow rate of the third gas or the like and controlling the particle size and density of the second film 303, the surface roughness of the first film 302 can be controlled. Thus, in the post-deposition seeding step, by adjusting the surface roughness of the first film 302, the embedding amount (state) of the third film 304 in the recess in the heat treatment step can be controlled.

[0128] By making the processing temperature in the post-deposition seeding step higher than the processing temperatures in the pre-deposition seed layer formation step and the film formation step, the surface state (surface roughness) of the third film 304 and the embedding amount in the recess in the heat treatment step can be controlled.

[0129] In the post-deposition seeding step, by supplying the second gas to the wafer 200, for example, outward diffusion of P from the first film 302 that occurs in the post-deposition seeding step can be suppressed.

[0130] Note that the heat treatment step in this aspect may not be performed. That is, the post-deposition seeding step may be performed to end the substrate processing in the substrate processing apparatus. The heat treatment step may be configured to be performed in another substrate processing apparatus. By ending at the post-deposition seeding step and not performing the heat treatment step, the time for temperature adjustment in the substrate processing apparatus that performs up to the post-deposition seeding step can be saved. The temperature adjustment time is the time taken to raise the temperature to the temperature at which the heat treatment step is performed and the time taken to lower the temperature after the heat treatment step is performed. By saving the temperature adjustment time, the substrate processing time in the substrate processing apparatus can be shortened. That is, the throughput of the substrate processing can be improved. On the other hand, when the post-deposition seeding step and the heat treatment step are performed in the same substrate processing apparatus, the occurrence of surface changes such as natural oxidation of the film existing on the wafer 200 can be suppressed.

[0131] <Other aspects of the present disclosure> As described above, the aspects of the present disclosure have been specifically described. However, the present disclosure is not limited to the above-described aspects, and various modifications can be made without departing from the gist thereof.

[0132] In the above aspect, in the seed layer formation step before film formation, the case where one of the two types of fourth gases is a halosilane-based gas and the other is a silane-based gas has been described as an example. However, the present disclosure is not limited thereto. In the present disclosure, for example, both of the two types of fourth gases may be halosilane-based gases. Even in this case, at least some of the effects described in the above aspect can be obtained. However, in this case, it is preferable to use different halosilane-based gases.

[0133] In the above second aspect, in the heat treatment step, the case where the second gas is not supplied to the wafer 200 has been described as an example. However, the present disclosure is not limited thereto. In the present disclosure, for example, in the heat treatment step of the above-described second aspect, a second gas containing P as a Group 15 element may be supplied. Even in this case, the same effect as that of the above-described second aspect can be obtained. In this aspect, further, by supplying the second gas in the heat treatment step and doping the first film 302 with P, for example, P that diffuses outward from the first film 302 in the heat treatment step can be supplemented.

[0134] However, in the heat treatment step of the above-described second aspect, the concentration of the second gas when the second gas is supplied is not limited to the second concentration exemplified as the concentration of the second gas in the heat treatment step of the above-described first aspect. Also, in the above-described second aspect, the concentration of the second gas in the film formation step and the concentration of the second gas in the heat treatment step may be the same concentration or different concentrations. In the above-described second aspect, the concentration of the second gas in the film formation step may be lower or higher than the concentration of the second gas in the heat treatment step. Even in these cases, at least some of the effects described in the above aspect can be obtained.

[0135] Although not particularly described in the above aspect, a temperature rising step of raising the temperature in the processing chamber 201 before performing the heat treatment step may be performed. At this time, for example, a second gas containing P as a group 15 element may be supplied. Even in this case, the same effects as those in the above-described aspect can be obtained. In this aspect, furthermore, for example, outward diffusion of P generated from the first film 302 by performing the temperature rising step can be suppressed.

[0136] In the above aspect, as the gas containing a group 14 element, a gas mainly containing Si has been described as an example, but the present disclosure is not limited thereto. For example, the present disclosure may use a gas containing Ge as the gas containing a group 14 element. Further, in the above aspect, as the second gas containing a group 15 or group 13 element, a gas mainly containing P, which is a group 15 element, has been described as an example, but the present disclosure is not limited thereto. For example, the present disclosure may use a gas containing any one of B, Al, Ga, and In as the gas containing a group 13 element. Even in these cases, the same effects as those in the above-described aspect can be obtained.

[0137] In the above aspect, an example of forming a Si-based film on the wafer 200 has been shown, but the present disclosure is not limited thereto. For example, the present disclosure can also be applied to the formation of a film containing a group 14 element. Examples of the film containing a group 14 element include a film mainly composed of at least one of Si, Ge, and SiGe.

[0138] The recipe used for each process is preferably prepared individually according to the process content, recorded and stored in the storage device 121c via a telecommunication line or an external storage device 123. Then, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe according to the process content from among a plurality of recipes recorded and stored in the storage device 121c. Thereby, it becomes possible to form films having various film types, composition ratios, film qualities, and film thicknesses with good reproducibility using a single substrate processing apparatus. In addition, the burden on the operator can be reduced, operation mistakes can be avoided, and each process can be started quickly.

[0139] The above recipe may be prepared not only when newly creating it, but also, for example, by modifying an existing recipe already installed in the substrate processing apparatus. When modifying the recipe, the modified recipe may be installed in the substrate processing apparatus via a telecommunication line or a recording medium on which the recipe is recorded. Further, the input / output device 122 provided in the existing substrate processing apparatus may be operated to directly modify the existing recipe already installed in the substrate processing apparatus.

[0140] In the above aspect, an example of forming a film using a batch-type substrate processing apparatus that processes a plurality of substrates at once has been described. The present disclosure is not limited to the above aspect, and can be suitably applied, for example, also when forming a film using a single-wafer-type substrate processing apparatus that processes one or several substrates at once. Further, in the above aspect, an example of forming a film using a substrate processing apparatus having a hot-wall type processing furnace has been described. The present disclosure is not limited to the above aspect, and can be suitably applied also when forming a film using a substrate processing apparatus having a cold-wall type processing furnace.

[0141] Even when using these substrate processing apparatuses, each process can be performed with the same processing procedures and processing conditions as those in the above aspect and modified examples, and the same effects as those in the above aspect and modified examples can be obtained.

[0142] The above aspect and modified examples can be used in appropriate combinations. The processing procedures and processing conditions at this time can be, for example, the same as the processing procedures and processing conditions of the above aspect and modified examples.

Explanation of Reference Numerals

[0143] 200 wafers (substrates) 302 First film

Claims

1. (a)A step of supplying a first gas containing a Group 14 element selected from Si and Ge to a substrate having a recess; (b)A step of supplying a second gas containing a Group 13 element selected from P or B as a Group 15 element, and Al, Ga, and In to the substrate; (c)With the second gas at a first concentration, by performing (a) and (b), a first film containing the Group 14 element is formed in the recess, and a step of stopping film formation before filling the inside of the recess with the first film; (d)After (c), performing (b) with the second gas at a second concentration lower than the first concentration, and a step of heat-treating the substrate; A substrate processing method comprising the steps.

2. In (d), a hydrogen-containing gas is supplied to the substrate. The substrate processing method according to Claim 1.

3. (a)A step of supplying a first gas containing a Group 14 element selected from Si and Ge to a substrate having a recess; (b)A step of supplying a second gas containing a Group 13 element selected from P or B as a Group 15 element, and Al, Ga, and In to the substrate; (c)With the second gas at a first concentration, by performing (a) and (b), a first film containing the Group 14 element is formed in the recess, and a step of stopping film formation before filling the inside of the recess with the first film; (d)After (c), performing (b) with the second gas at a second concentration and supplying a hydrogen-containing gas to the substrate to heat-treat the substrate; Comprising the steps, In (d), the pressure in the space where the substrate is present is made lower than the pressure in the space in (c). A substrate processing method.

4. In (d), the pressure in the space where the substrate is present is made lower than the pressure in the space in (c). The substrate processing method according to Claim 2.

5. In (d), an inert gas is supplied to the substrate. The substrate processing method according to Claim 1.

6. (e)After (c), further comprising a step of supplying a third gas containing the Group 14 element to the substrate to form a second film containing the Group 14 element on the surface of the recess. The substrate processing method according to Claim 1.

7. The third gas supplied in (e) is a hydrogen compound. The substrate processing method according to Claim 6.

8. The hydrogen compound does not contain halogen. The substrate processing method according to Claim 7.

9. (a) A step of supplying a first gas containing a Group 14 element selected from Si and Ge to a substrate having a recess; (b) A step of supplying a second gas containing a Group 13 element selected from P or B as a Group 15 element and Al, Ga, and In to the substrate; (c) With the second gas at a first concentration, performing (a) and (b) to form a first film containing the Group 14 element in the recess, and stopping film formation before filling the inside of the recess with the first film; (d) After (c), performing (b) with the second gas at a second concentration and heat-treating the substrate; (e) After (c), supplying a third gas containing the Group 14 element to the substrate and forming a second film containing the Group 14 element on the surface of the recess; which comprises; in (e), further supplying the second gas, A substrate processing method.

10. The second film formed in (e) is formed discontinuously. The substrate processing method according to Claim 6.

11. (f) Before (c), further comprising a step of supplying a fourth gas containing the Group 14 element to the substrate and forming a seed layer containing the Group 14 element on the surface of the recess. The substrate processing method according to Claim 1.

12. (f) Before (c), further comprising a step of supplying a fourth gas containing the Group 14 element to the substrate and forming a seed layer containing the Group 14 element on the surface of the recess. The substrate processing method according to Claim 6.

13. The temperature of the substrate in (f) is lower than the temperature of the substrate in (e). The substrate processing method according to Claim 12.

14. The fourth gas used in (f) and the third gas used in (e) are different compounds. The substrate processing method according to Claim 13.

15. In (f), a gas containing a halogen is used as the fourth gas. In (e), a gas not containing a halogen is used as the third gas. The substrate processing method according to Claim 14.

16. In (f), a gas containing a halogen is used as the fourth gas. The substrate processing method according to Claim 11.

17. The temperature of the substrate when performing (f) is lower than the temperature of the substrate when performing (c). The substrate processing method according to Claim 11.

18. (g) Having a step of raising the temperature between (c) and (d). The substrate processing method according to Claim 1.

19. Supplying the second gas to the substrate in (g). The substrate processing method according to claim 18.

20. (a) A step of supplying a first gas containing a Group 14 element selected from Si and Ge to a substrate having a concave portion; (b) A step of supplying a second gas containing a Group 13 element selected from P or B as a Group 15 element, and Al, Ga, and In to the substrate; (c) A step of forming a first film containing the Group 14 element in the concave portion by performing (a) and (b) with the second gas at a first concentration, and stopping film formation before filling the inside of the concave portion with the first film; (d) After (c), a step of performing (b) with the second gas at a second concentration lower than the first concentration, and heat-treating the substrate; A method for manufacturing a semiconductor device having the above steps.

21. (a) A procedure of supplying a first gas containing a Group 14 element selected from Si and Ge to a substrate having a concave portion; (b) A procedure of supplying a second gas containing a Group 13 element selected from P or B as a Group 15 element, and Al, Ga, and In to the substrate; (c) A procedure of forming a first film containing the Group 14 element in the concave portion by performing (a) and (b) with the second gas at a first concentration, and stopping film formation before filling the inside of the concave portion with the first film; (d) After (c), a procedure of performing (b) with the second gas at a second concentration lower than the first concentration, and heat-treating the substrate; A program for causing a computer to execute the above procedures on a substrate processing apparatus.

22. A first gas supply system for supplying a first gas containing a Group 14 element selected from Si and Ge to a substrate having a concave portion; A second gas supply system for supplying a second gas containing a Group 13 element selected from P or B as a Group 15 element, and Al, Ga, and In to the substrate; A heating mechanism for heating the substrate; (a) A process of supplying the first gas to the substrate; (b) A process of supplying the second gas to the substrate; (c) A process of forming a first film containing the Group 14 element in the concave portion by performing (a) and (b) with the second gas at a first concentration, and stopping film formation before filling the inside of the concave portion with the first film; After (d) and (c), the first gas supply system, the second gas supply system, and the heating mechanism are configured to be controllable such that the second gas is set to a second concentration lower than the first concentration and (b) is performed, and a process of heat-treating the substrate is performed. A substrate processing apparatus having the same. **Claim 23**: (a) A step of supplying a first gas containing a Group 14 element selected from Si and Ge to a substrate having a concave portion; (b) A step of supplying a second gas containing a Group 13 element selected from P or B as a Group 15 element, and Al, Ga, and In to the substrate; (c) A step of forming a first film containing the Group 14 element in the concave portion by performing (a) and (b) with the second gas at a first concentration, and stopping film formation before filling the inside of the concave portion with the first film; (d) After (c), a step of performing (b) with the second gas at a second concentration and supplying a hydrogen-containing gas to the substrate to heat-treat the substrate; having the same; In (d), the pressure in the space where the substrate is present is made lower than the pressure in the space in (c). A method for manufacturing a semiconductor device. **Claim 24**: (a) A procedure of supplying a first gas containing a Group 14 element selected from Si and Ge to a substrate having a concave portion; (b) A procedure of supplying a second gas containing a Group 13 element selected from P or B as a Group 15 element, and Al, Ga, and In to the substrate; (c) A procedure of forming a first film containing the Group 14 element in the concave portion by performing (a) and (b) with the second gas at a first concentration, and stopping film formation before filling the inside of the concave portion with the first film; (d) After (c), a procedure of performing (b) with the second gas at a second concentration and supplying a hydrogen-containing gas to the substrate to heat-treat the substrate; (d) A procedure of making the pressure in the space where the substrate is present lower than the pressure in the space in (c); A program for causing a computer to execute the same in a substrate processing apparatus. **Claim 25**: A first gas supply system that supplies a first gas containing a Group 14 element selected from Si and Ge to a substrate having a concave portion; A second gas supply system that supplies a second gas containing a Group 13 element selected from P or B as a Group 15 element, and Al, Ga, and In to the substrate; A heating mechanism that heats the substrate; (a) A process of supplying the first gas to the substrate; (b) a process of supplying the second gas to the substrate; (c) a process of forming a first film containing a Group 14 element in the recess by performing (a) and (b) with the second gas at a first concentration, and stopping film formation before filling the inside of the recess with the first film; (d) after (c), performing (b) with the second gas at a second concentration and heat-treating the substrate by supplying a hydrogen-containing gas to the substrate; (d) a control unit configured to be able to control the first gas supply system, the second gas supply system, and the heating mechanism so as to perform a process of making the pressure in the space where the substrate exists lower than the pressure in the space in (c); A substrate processing apparatus having the above.

26. (a) A step of supplying a first gas containing a Group 14 element selected from Si and Ge to a substrate having a recess; (b) a step of supplying a second gas containing a Group 13 element selected from P or B as a Group 15 element and Al, Ga, and In to the substrate; (c) a step of forming a first film containing a Group 14 element in the recess by performing (a) and (b) with the second gas at a first concentration, and stopping film formation before filling the inside of the recess with the first film; (d) after (c), performing (b) with the second gas at a second concentration and heat-treating the substrate; (e) after (c), a step of supplying a third gas containing a Group 14 element and the second gas to the substrate to form a second film containing a Group 14 element on the surface of the recess; A method for manufacturing a semiconductor device having the above.

27. (a) A procedure of supplying a first gas containing a Group 14 element selected from Si and Ge to a substrate having a recess; (b) a procedure of supplying a second gas containing a Group 13 element selected from P or B as a Group 15 element and Al, Ga, and In to the substrate; (c) a procedure of forming a first film containing a Group 14 element in the recess by performing (a) and (b) with the second gas at a first concentration, and stopping film formation before filling the inside of the recess with the first film; (d) after (c), performing (b) with the second gas at a second concentration and heat-treating the substrate; (e) after (c), a procedure of supplying a third gas containing a Group 14 element and the second gas to the substrate to form a second film containing a Group 14 element on the surface of the recess; A program for causing a computer to execute a substrate processing apparatus.

28. A first gas supply system for supplying a first gas containing a Group 14 element selected from Si and Ge to a substrate having a recess, A second gas supply system for supplying a second gas containing a Group 13 element selected from P or B as a Group 15 element, Al, Ga, and In to the substrate, A heating mechanism for heating the substrate, (a) A process of supplying the first gas to the substrate, (b) A process of supplying the second gas to the substrate, (c) With the second gas at a first concentration, by performing (a) and (b), a first film containing the Group 14 element is formed in the recess, and a process of stopping film formation before filling the inside of the recess with the first film, (d) After (c), performing (b) with the second gas at a second concentration and a process of heat-treating the substrate, (e) After (c), supplying a third gas containing the Group 14 element and the second gas to the substrate, and a process of forming a second film containing the Group 14 element on the surface of the recess, a control unit configured to be able to control the first gas supply system, the second gas supply system, and the heating mechanism so as to perform the processes, A substrate processing apparatus having the same.

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