SUBSTRATE PROCESSING METHOD, SUBSTRATE PROCESSING APPARATUS, PROGRAM, AND SEMICONDUCTOR DEVICE MANUFACTURING METHOD

Abstract

The present invention provides a technology which performs: (a) a step for supplying a group 14 element-containing gas to a substrate; and (e) a step for performing a cycle a predetermined number of times after the step (a), the cycle sequentially comprising (b) a step for supplying a dopant gas, which contains a halide of a group 13 element or a group 15 element, to the substrate, (c) a step for supplying a first reducing gas to the substrate, and (d) a step for supplying the group 14 element-containing gas to the substrate in this order.

Description

[Technical field]

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

[0002] 2. Description of the Related Art As one step in the manufacturing process of a semiconductor device, a process of forming a film on a substrate is sometimes performed (see, for example, Japanese Patent Application Laid-Open No. 2010-118462). Summary of the Invention [Problem to be solved by the invention]

[0003] An object of the present disclosure is to provide a technique capable of forming a film with small surface roughness on a substrate, the film being doped with a Group 13 element or Group 15 element and containing a Group 14 element as a main element. [Means for solving the problem]

[0004] According to one aspect of the present disclosure, (a) supplying a Group 14 element-containing gas to a substrate; (e) performing a cycle including, in this order, a predetermined number of cycles after (a), the cycles including (b) supplying to the substrate a dopant gas containing a halide of a Group 13 element or a Group 15 element, (c) supplying to the substrate a first reducing gas, and (d) supplying to the substrate a Group 14 element-containing gas; Techniques for doing so are provided. Effect of the Invention

[0005] According to the present disclosure, it is possible to form a film with small surface roughness on a substrate. [Brief description of the drawings]

[0006] [Figure 1]FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, showing a processing furnace 202 portion in vertical cross section. [Diagram 2] FIG. 2 is a schematic configuration diagram of a portion of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a cross-sectional view of the processing furnace 202 taken along line AA in FIG. [Diagram 3] FIG. 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a block diagram showing a control system of the controller 121. [Figure 4] FIG. 5 is a flow diagram showing a processing sequence according to one embodiment of the present disclosure. [Diagram 5] FIG. 4 is a diagram showing a processing sequence according to an embodiment of the present disclosure. [Figure 6] FIG. 6 is a plan view showing a portion of a substrate used in one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] <One aspect of the present disclosure> Hereinafter, one embodiment of the present disclosure will be described with reference to Figures 1 to 6. Note that all of the drawings used in the following description are schematic, and the dimensional relationships of the elements, the ratios of the elements, and the like shown in the drawings do not necessarily match those in reality. Furthermore, the dimensional relationships of the elements, the ratios of the elements, and the like between multiple drawings do not necessarily match.

[0008] (1) Configuration of the substrate processing device 1, the process furnace 202 has a heater 207 as a temperature regulator (heating unit). The heater 207 is cylindrical and is installed vertically by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas by heat.

[0009] A reaction tube 203 is disposed concentrically with the heater 207 inside the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and is formed in a cylindrical shape with a closed upper end and an open lower end. A manifold 209 is disposed concentrically with the reaction tube 203 below the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS) and is formed in a cylindrical shape with an open upper end and a closed lower end. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a seal member. The reaction tube 203 is installed vertically like the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel). A processing chamber 201 is formed in a cylindrical hollow portion of the processing vessel. The processing chamber 201 is configured to be capable of accommodating a wafer 200 as a substrate. In the processing chamber 201, processing of the wafer 200 is performed.

[0010] In the processing chamber 201, nozzles 249a to 249e as first to fifth supply units are provided so as to penetrate the sidewall of the manifold 209. Gas supply pipes 232a to 232e are connected to the nozzles 249a to 249e, respectively. The nozzles 249a to 249e are different nozzles, and the nozzles 249b and 249d are provided adjacent to the nozzle 249c. The nozzles 249a and 249e are provided adjacent to the opposite side of the nozzles 249b and 249d adjacent to the nozzle 249c.

[0011] Gas supply pipes 232a-232e are provided with mass flow controllers (MFCs) 241a-241e, which are flow rate controllers (flow rate control parts), and valves 243a-243e, which are on-off valves, in order from the upstream side of the gas flow. Gas supply pipes 232f-232j are connected to the gas supply pipes 232a-232e downstream of the valves 243a-243e, respectively. Gas supply pipes 232f-232j are provided with MFCs 241f-241j and valves 243f-243j in order from the upstream side of the gas flow, respectively. Gas supply pipes 232a-232e are made of, for example, a metal material such as SUS.

[0012] As shown in FIG. 2, the nozzles 249a to 249e are provided in a circular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, from the lower part to the upper part of the inner wall of the reaction tube 203, so as to rise upward in the arrangement direction of the wafers 200. That is, the nozzles 249a to 249e are provided in a region horizontally surrounding the wafer arrangement region on the side of the wafer arrangement region in which the wafers 200 are arranged, so as to extend along the wafer arrangement region. In a plan view, the nozzle 249c is disposed so as to face an exhaust port 231a (described later) on a straight line across the center of the wafer 200 loaded into the processing chamber 201. The nozzles 249b and 249d are disposed so as to sandwich a straight line L passing through the nozzle 249c and the center of the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer periphery of the wafers 200). Moreover, the nozzles 249a and 249e are arranged on both sides of the nozzle 249b and the nozzle 249d opposite to the side adjacent to the nozzle 249c along the inner wall of the reaction tube 203. The straight line L is also a straight line passing through the nozzle 249c and the center of the wafer 200. That is, the nozzle 249d can be said to be provided on the opposite side of the nozzle 249b across the straight line L. The nozzle 249e can be said to be provided on the opposite side of the nozzle 249a across the straight line L. The nozzles 249b and 249d are arranged in line symmetry with the straight line L as the axis of symmetry. The nozzles 249a and 249e are arranged in line symmetry with the straight line L as the axis of symmetry. Gas supply holes 250a to 250e for supplying gas are provided on the side surfaces of the nozzles 249a to 249e, respectively. The gas supply holes 250a to 250e are each open to face (oppose) the exhaust port 231a in a plan view, and are capable of supplying gas toward the wafers 200. A plurality of the gas supply holes 250a to 250e are provided from the lower part to the upper part of the reaction tube 203.

[0013] A Group 14 element-containing gas is supplied as a processing gas from the gas supply pipe 232a into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.

[0014] A dopant gas containing a halide of a Group 13 element or a Group 15 element is supplied from the gas supply pipe 232b into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.

[0015] A first reducing gas is supplied as a reducing gas from the gas supply pipe 232c into the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c.

[0016] A first halosilane-based gas is supplied as a processing gas from the gas supply pipe 232d into the processing chamber 201 via the MFC 241d, a valve 243d, and a nozzle 249d.

[0017] A second halosilane-based gas is supplied as a processing gas from the gas supply pipe 232e into the processing chamber 201 via the MFC 241e, the valve 243e, and the nozzle 249e.

[0018] From the gas supply pipes 232f to 232j, an inert gas is supplied 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, into the processing chamber 201. The inert gas acts as a purge gas, a carrier gas, a dilution gas, or the like.

[0019] A processing gas supply system is mainly composed of the gas supply pipes 232a, 232d, and 232e, the MFCs 241a, 241d, and 241e, and the valves 243a, 243d, and 243e. The gas supply pipe 232b, the MFC 241b, and the valve 243b may be included in the processing gas supply system. A reducing gas supply system is mainly composed of the gas supply pipe 232c, the MFC 241c, and the valve 243c. An inert gas supply system is mainly composed of the gas supply pipes 232f to 232j, the MFCs 241f to 241j, and the valves 243f to 243j. In this disclosure, the gas supply system including the gas supply pipe 232a, the MFC 241a, and the valve 243a is also referred to as a first supply system. The gas supply pipe 232f, the MFC 241f, and the valve 243f may be considered to be included in the first supply system. A gas supply system including the gas supply pipe 232b, the MFC 241b, and the valve 243b may also be referred to as a second supply system. The gas supply pipe 232g, the MFC 241g, and the valve 243g may also be considered to be included in the second supply system. A gas supply system including the gas supply pipe 232c, the MFC 241c, and the valve 243c may also be referred to as a third supply system. The gas supply pipe 232h, the MFC 241h, and the valve 243h may also be considered to be included in the third supply system. A gas supply system including the gas supply pipe 232d, the MFC 241d, and the valve 243d may also be referred to as a third supply system. The gas supply pipe 232i, the MFC 241i, and the valve 243i may also be considered to be included in the third supply system. The gas supply system including the gas supply pipe 232e, the MFC 241e, and the valve 243e is also referred to as a third supply system. The gas supply pipe 232j, the MFC 241j, and the valve 243j may be considered to be included in the third supply system.

[0020] Any or all of the various supply systems described above may be configured as an integrated supply system 248 in which the valves 243a-243j and the MFCs 241a-241j are integrated. The integrated supply system 248 is connected to the gas supply pipes 232a-232j, and the supply operation of various gases into the gas supply pipes 232a-232j, i.e., the opening and closing operation of the valves 243a-243j and the flow rate adjustment operation by the MFCs 241a-241j, are controlled by a controller 121, which will be described later. The integrated supply system 248 is configured as an integrated or separate integrated unit, and can be attached and detached to and from the gas supply pipes 232a-232j, etc., in units of integrated units, and is configured so that maintenance, replacement, expansion, etc. of the integrated supply system 248 can be performed in units of integrated units.

[0021] An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided at the lower side of the side wall of the reaction tube 203. As shown in FIG. 2, the exhaust port 231a is provided at a position facing the nozzles 249a to 249e (gas supply holes 250a to 250e) across the wafer 200 in a plan view. The exhaust port 231a may be provided along the side wall of the reaction tube 203 from the lower part to the upper part, 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 adjustment unit). The APC valve 244 can evacuate and stop the evacuation of the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating, and further, can adjust the pressure inside the processing chamber 201 by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating. An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may be included in the exhaust system.

[0022] Below the manifold 209, a seal cap 219 is provided as a furnace port cover body capable of airtightly closing the lower end opening of the manifold 209. The seal cap 219 is made of a metal material such as SUS, and is formed in a disk shape. An O-ring 220b is provided on the upper surface of the seal cap 219 as a seal member that abuts against the lower end of the manifold 209. Below the seal cap 219, a rotation mechanism 267 is provided for rotating the boat 217, which will be described later. A rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217 through the seal cap 219. The rotation mechanism 267 is configured to rotate the wafers 200 by rotating the boat 217. The seal cap 219 is configured to be vertically raised and lowered by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203. The boat elevator 115 is configured as a transfer device (transfer mechanism) that transfers (transports) the wafers 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219. A shutter 219s is provided below the manifold 209 as a furnace port cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is transported out of the processing chamber 201. The shutter 219s is made of a metal material such as SUS and is formed in a disk shape. An O-ring 220c is provided on the upper surface of the shutter 219s as a seal member that contacts the lower end of the manifold 209. The opening and closing operation (lifting and lowering operation, rotating operation, etc.) of the shutter 219s is controlled by a shutter opening and closing mechanism 115s.

[0023] The boat 217 as a substrate support is configured to support a plurality of wafers 200, for example 25 to 200, in multiple stages in a horizontal position and aligned vertically with their centers aligned, i.e., arranged at intervals. The boat 217 is made of a heat-resistant material such as quartz or SiC. At the bottom of the boat 217, heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages.

[0024] A temperature sensor 263 serving as a temperature detector is installed in the reaction tube 203. By adjusting the power supply to the heater 207 based on temperature information detected by the temperature sensor 263, the temperature distribution in the process chamber 201 becomes a desired one. The temperature sensor 263 is installed along the inner wall of the reaction tube 203.

[0025] 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, for example, a touch panel, is connected to the controller 121.

[0026] The storage device 121c is composed of, for example, a flash memory, a hard disk drive (HDD), a solid state drive (SSD), etc. A control program for controlling the operation of the substrate processing apparatus, a process recipe in which procedures and conditions of the substrate processing described later are described, etc. are readably stored in the storage device 121c. The process recipe is a combination of procedures in the substrate processing described later that are executed by the controller 121 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. In addition, the process recipe is also simply referred to as a recipe. When the word program is used in this disclosure, it may include only a recipe, only a control program, or both. The RAM 121b is configured as a memory area (work area) in which the programs, data, etc. read by the CPU 121a are temporarily stored.

[0027] The I / O port 121d is connected to the above-mentioned 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, and the like.

[0028] The CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to an input of an operation command from the input / output device 122, etc. The CPU 121a is configured to be capable of controlling the flow rate adjustment operation of 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 and the pressure adjustment operation by the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the lifting and lowering operation of the boat 217 by the boat elevator 115, the opening and closing operation of the shutter 219s by the shutter opening and closing mechanism 115s, etc., in accordance with the contents of the read recipe.

[0029] The controller 121 can be configured by installing the above-mentioned program stored in the external storage device 123 in 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 USB memory, a semiconductor memory such as an SSD, and the like. The storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media. When the term recording media is used in this disclosure, it may include only the storage device 121c alone, only the external storage device 123 alone, or both of them. The program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.

[0030] (2) Substrate processing An example of a processing sequence for forming a film on a substrate as one step in a manufacturing process of a semiconductor device using the above-mentioned substrate processing apparatus will be described mainly with reference to Figures 4 and 5. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by a controller 121.

[0031] In the processing sequence shown in Figs. Step A of supplying a Group 14 element-containing gas to a wafer 200 as a substrate; a step E of performing a cycle including, in this order, a step B of supplying a dopant gas containing a halide of a group 13 element or a group 15 element to the wafer 200, a step C of supplying a first reducing gas to the wafer 200, and a step D of supplying a group 14 element-containing gas to the wafer 200 a predetermined number of times (n times, n is an integer of 2 or more) after the step A; Do the following. Furthermore, after step E, step F is performed in which a Group 14 element-containing gas is supplied to the wafer 200. This performs a step (film formation step) of forming a film containing a Group 14 element as a main element to which a Group 13 element or a Group 15 element is added (doped) on the wafer 200. In the present disclosure, a film doped with a Group 13 element or a Group 15 element and containing a Group 14 element as a main element is also referred to as a doped film.

[0032] Specifically, in the film formation step, Step A of supplying a Group 14 element-containing gas as a processing gas to the wafer 200 from a nozzle 249a; a step B of supplying a dopant gas containing a halide of a Group 13 element or a Group 15 element as a dopant gas from a nozzle 249b to the wafer 200, a step C of supplying a first reducing gas from a nozzle 249c to the wafer 200, and a step A of supplying a Group 14 element-containing gas as a process gas from the nozzle 249a to the wafer 200 in this order, a step E of performing a cycle including these steps a predetermined number of times after the step A; Do the following. Furthermore, step F is performed in which a Group 14 element-containing gas is supplied as a processing gas to the wafer 200 from the nozzle 249a.

[0033] 4 and 5, before step A, step G of supplying two types of halosilane-based gases to the wafer 200 is performed. As a result, a step of forming a seed layer on the wafer 200 (seed layer formation step) is performed.

[0034] Specifically, in the seed layer formation step, Before step A, a step G1 of supplying a first halosilane-based gas to the wafer 200 from a nozzle 249d; After step 1, step G2 is performed in which a second halosilane-based gas different from the first halosilane-based gas is supplied to the wafer 200 from the nozzle 249e.

[0035] In this disclosure, the above-described film formation sequence may be expressed as follows for convenience. Similar notations will be used in the following explanations of modified examples, etc.

[0036] First halosilane gas → second halosilane gas → Group 14 element-containing gas → (dopant gas containing a halide of a Group 13 element or a Group 15 element → first reducing gas → Group 14 element-containing gas)×n → Group 14 element-containing gas

[0037] In this disclosure, the term "wafer" may refer to the wafer itself or a laminate of the wafer and a predetermined layer or film formed on the surface thereof. In this disclosure, the term "surface of the wafer" may refer to the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer. In this disclosure, the term "forming a predetermined layer on a wafer" may refer to forming a predetermined layer directly on the surface of the wafer itself or forming a predetermined layer on a layer or the like formed on the wafer. In this disclosure, the term "substrate" is synonymous with the term "wafer".

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

[0039] (Pressure and temperature regulation) The inside of the processing chamber 201, i.e., the space in which the wafer 200 is present, is evacuated (reduced pressure exhaust) by the vacuum pump 246 so that the pressure inside the processing chamber 201 is a desired pressure (vacuum level). At this time, the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. Also, the wafer 200 inside the processing chamber 201 is heated by the heater 207 so that the temperature inside the processing chamber 201 is a desired film formation temperature. At this time, the power supply to the heater 207 is feedback-controlled based on temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution. Also, the rotation mechanism 267 starts rotating the wafer 200. The evacuation inside the processing chamber 201 and the heating and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.

[0040] (Seed layer formation step) Thereafter, as a seed layer forming step, steps, that is, step G1 of supplying a first halosilane-based gas and step G2 of supplying a second halosilane-based gas different from the first halosilane-based gas, are sequentially performed.

[0041] [Step G1] In this step, a first halosilane-based gas is supplied to the wafer 200 in the processing chamber 201 from the nozzle 249d, and an inert gas is supplied to the wafer 200 from each of the nozzles 249a to 249c and 249e.

[0042] Specifically, the valve 243d is opened to allow a first halosilane-based gas to flow into the gas supply pipe 232d. The first halosilane-based gas has a flow rate adjusted by the MFC 241d, is supplied into the processing chamber 201 via the nozzle 249d, and is exhausted from the exhaust port 231a. At this time, the first halosilane-based gas is supplied to the wafer 200. At this time, the valves 243f to 243h, 243j are opened to supply an inert gas into the processing chamber 201 via each of the nozzles 249a to 249c, 249e.

[0043] By supplying the first halosilane-based gas to the wafer 200 under processing conditions described below, the treatment action (etching action) of the first halosilane-based gas can remove native oxide films, impurities, and the like from the surface of the wafer 200, making it possible to clean this surface.

[0044] After the surface of the wafer 200 is cleaned, the valve 243d is closed to stop the supply of the halosilane-based gas into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove gas remaining in the processing chamber 201 from the processing chamber 201. At this time, the valves 243f to 243j are opened to supply an inert gas 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, thereby purging the processing chamber 201 (purge step).

[0045] As the first halosilane-based gas, for example, a chlorosilane-based gas such as dichlorosilane (SiH2Cl2, abbreviated as DCS) gas, monochlorosilane (SiH3Cl, abbreviated as MCS) gas, tetrachlorosilane (SiCl4, abbreviated as STC) gas, trichlorosilane (SiHCl3, abbreviated as TCS) gas, hexachlorodisilane (Si2Cl6, abbreviated as HCDS) gas, or octachlorotrisilane (Si3Cl8, abbreviated as OCTS) gas can be used. As the first halosilane-based gas, for example, a tetrafluorosilane (SiF4) gas, tetrabromosilane (SiBr4) gas, or tetraiodosilane (SiI4) gas can be used. That is, as the first halosilane-based gas, for example, a halosilane-based gas such as a fluorosilane-based gas, a bromosilane-based gas, or an iodosilane-based gas can be used in addition to a chlorosilane-based gas.

[0046] [Step G2] After step G1 is completed, a second halosilane-based gas is supplied from nozzle 249e to wafer 200 in processing chamber 201, ie, to the surface of cleaned wafer 200, and an inert gas is supplied from each of nozzles 249a to 249d.

[0047] Specifically, the valve 243e is opened to allow the second halosilane-based gas to flow into the gas supply pipe 232e. The second halosilane-based gas has a flow rate adjusted by the MFC 241e, is supplied into the processing chamber 201 via the nozzle 249e, and is exhausted from the exhaust port 231a. At this time, the second halosilane-based gas is supplied to the wafers 200. At this time, the valves 243f to 243i are opened to supply an inert gas into the processing chamber 201 via each of the nozzles 249a to 249d.

[0048] By supplying the second halosilane-based gas to the wafer 200 under processing conditions described below, the Si element contained in the second halosilane-based gas can be adsorbed onto the surface of the wafer 200 cleaned in step G1, thereby forming seeds (nuclei). Under the processing conditions described below, the crystal structure of the nuclei formed on the surface of the wafer 200 is amorphous.

[0049] After the nuclei are formed on the surfaces of the wafers 200, the valve 243e is closed to stop the supply of the second halosilane-based gas into the processing chamber 201. Then, gases remaining in the processing chamber 201 are purged from the processing chamber 201 by a processing procedure similar to that of the purging step of step G1.

[0050] As the second halosilane-based gas, the halosilane-based gas described above for the first halosilane-based gas can be used.

[0051] The processing conditions in step G1 are as follows: First halosilane gas supply flow rate: 100 to 1000 sccm First halosilane gas supply time: 1 to 30 minutes Inert gas supply flow rate (per gas supply pipe): 1000~3000sccm Treatment temperature (first temperature): 300 to 500°C Processing pressure: 2~1000Pa Examples are given below.

[0052] The processing conditions in step G2 are as follows: First halosilane gas or second reducing gas supply flow rate: 50 to 1000 sccm Supply time of first halosilane gas or second reducing gas: 10 seconds to 5 minutes The other processing conditions are the same as those in step G1.

[0053] Here, in this disclosure, when a numerical range such as "2 to 1000 Pa" is expressed, it means that the lower limit and the upper limit are included in the range. Thus, for example, "2 to 1000 Pa" means "2 Pa or more and 1000 Pa or less". The same applies to other numerical ranges. Note that the process temperature means the temperature of the wafer 200, and the process pressure means the pressure inside the process chamber 201. Furthermore, a gas supply flow rate of 0 sccm means that the gas is not supplied. These also apply to the following explanations.

[0054] As the inert gas, for example, rare gas such as N2 gas, Ar gas, He gas, Ne gas, Xe gas, etc. This also applies to the temperature increasing step and the film forming step described later.

[0055] (Heating step) After the seed layer formation step is completed, the output of the heater 207 is adjusted so as to change the temperature inside the processing chamber 201 to a second temperature higher than the first temperature. When performing this step, the valves 243f to 243j are opened, and an inert gas is supplied into the processing chamber 201 through the nozzles 249a to 249e to purge the inside of the processing chamber 201. After the temperature inside the processing chamber 201 reaches the second temperature and becomes stable, the film formation step described below is started.

[0056] (Membrane formation step) As a film formation step, A step A of supplying a group 14 element-containing gas; a step E of performing a cycle including, in this order, a step B of supplying a dopant gas containing a halide of a group 13 element or a group 15 element, a step C of supplying a first reducing gas, and a step D of supplying a group 14 element-containing gas a predetermined number of times after the step A; are executed sequentially. Furthermore, after step E, step F is carried out in which a group 14 element-containing gas is supplied.

[0057] [Step A] In this step, a Group 14 element-containing gas is supplied from the nozzle 249a to the wafer 200 in the processing chamber 201, that is, to the surface of the seed layer formed on the wafer 200, and an inert gas is supplied from each of the nozzles 249b to 249e.

[0058] Specifically, the valve 243a is opened to allow a Group 14 element-containing gas to flow into the gas supply pipe 232a. The Group 14 element-containing gas is adjusted in flow rate by the MFC 241a, supplied into the processing chamber 201 through the nozzle 249a, and exhausted from the exhaust port 231a. At this time, the valves 243g to 243j are opened to supply an inert gas into the processing chamber 201 through each of the nozzles 249b to 249e.

[0059] By supplying a Group 14 element-containing gas to the wafer 200 from the nozzle 249a under processing conditions described below, a film containing a Group 14 element as a main element can be formed on the surface of the wafer 200, i.e., on the seed layer formed on the wafer 200.

[0060] The processing conditions in step A are as follows: Flow rate of Group 14 element-containing gas: 100 to 3000 sccm Group 14 element-containing gas supply time: 1 to 30 minutes Inert gas supply flow rate (per gas supply pipe): 100~2000sccm Treatment temperature (second temperature): 300~600℃ Processing pressure: 1~1000Pa The process conditions shown here are conditions under which the Group 14 element-containing gas is thermally decomposed when the Group 14 element-containing gas exists alone in the process chamber 201, that is, conditions under which a CVD reaction occurs. That is, the process conditions shown here are conditions under which the adsorption (deposition) of the Group 14 element onto the wafer 200 is not self-limited, that is, conditions under which the adsorption of the Group 14 element onto the wafer 200 is non-self-limited.

[0061] Examples of the Group 14 element-containing gas include monosilane (SiH4, abbreviated as MS) gas, disilane (Si2H6, abbreviated as DS) gas, trisilane (Si3H8) gas, and tetrasilane (Si4H 10 ) gas, pentasilane (SiH 12 ) gas, hexasilane (Si6H 14) gas, germane (GeH4) gas, digermane (Ge2H6) gas, trigermane (Ge3H8) gas, tetragermane (Ge4H 10 ) Gas, Pentagermane (Ge5H 12 ) gas, hexagermane (Ge6H 14 ) gas can be used. The Group 14 element-containing gas is preferably, for example, any one of monosilane (SiH4, abbreviated as MS) gas, disilane (Si2H6, abbreviated as DS) gas, trisilane (Si3H8) gas, germane (GeH4) gas, digermane (Ge2H6) gas, and trigermane (Ge3H8) gas. These react (decompose) relatively easily, and therefore can improve the film formation speed.

[0062] [Step E] In step E, a cycle including the following steps B, C, and D in this order is performed a predetermined number of times (n times, n is an integer of 2 or more). This makes it possible to form on the wafer 200 a film that is doped with a Group 13 element or Group 15 element, contains a Group 14 element as a main element, and has small surface roughness.

[0063] [Step B] After step A is completed, a dopant gas containing a halide of a Group 13 element or a Group 15 element is supplied from nozzle 249b to the wafer 200 in the processing chamber 201, i.e., to the surface of the film formed on the wafer 200 and containing a Group 14 element as a main element, and an inert gas is supplied from each of nozzles 249a, 249c to 249e.

[0064] Specifically, the valve 243b is opened to allow the dopant gas to flow into the gas supply pipe 232b. The dopant gas is adjusted in flow rate by the MFC 241b, supplied into the processing chamber 201 through the nozzle 249b, and exhausted from the exhaust port 231a. At this time, the valves 243f, 243h to 243j are opened to supply the inert gas into the processing chamber 201 through the nozzles 249a, 249c to 249e, respectively.

[0065] By supplying a dopant gas to the wafer 200 from the nozzle 249b under processing conditions described below, a film containing a halide of a Group 13 element or a Group 15 element as a main component can be formed on the film formed on the wafer 200 and containing a Group 14 element as a main element.

[0066] As the dopant gas containing a halide of a Group 13 element, a gas containing a Group 13 element that becomes a solid by itself (such as boron (B)) such as trichloroborane (BCl3) gas can be used. In addition, as a dopant gas containing a halide of a Group 15 element, for example, a gas containing a Group 15 element that becomes a solid by itself (P, arsenic (As), etc.), such as phosphorus trichloride (PCl3) gas, can be used.

[0067] The dopant gas preferably contains the element B. For example, by using a BCl3-containing gas, a film can be easily formed even if the surface of the wafer 200 has a fine structure.

[0068] As the dopant gas, one containing Cl element in addition to B element is preferable. For example, Cl element of BCl3 adsorbed on the film containing Group 14 element as a main element inhibits the adsorption of Group 14 element-containing gas to the film, but it is easily reduced in step C and the Cl element is desorbed. Therefore, in steps D and F, the adsorption of Group 14 element-containing gas to the film is promoted, and the film formation speed can be improved.

[0069] [Step C] After step B is completed, a first reducing gas is supplied from nozzle 249c to the wafer 200 in the processing chamber 201, i.e., to the surface of the film formed on the wafer 200 and containing as its main component a halide of a Group 13 element or a Group 15 element, and an inert gas is supplied from each of nozzles 249a, 249b, 249d, and 249e.

[0070] Specifically, the valve 243c is opened to allow the first reducing gas to flow into the gas supply pipe 232c. The first reducing gas is adjusted in flow rate by the MFC 241c, supplied into the processing chamber 201 through the nozzle 249c, and exhausted from the exhaust port 231a. At this time, the valves 243f, 243g, 243i, and 243j are opened to supply the inert gas into the processing chamber 201 through the nozzles 249a, 249b, 249d, and 249e, respectively.

[0071] By supplying a first reducing gas to the wafer 200 from the nozzle 249c under processing conditions to be described later, it is possible to reduce and remove halogen elements from a film containing a halide of a Group 13 element or a Group 15 element as a main component on the surface of the wafer 200, i.e., formed on the wafer 200. This makes it possible to form a film containing a Group 13 element or a Group 15 element as a main element.

[0072] The first reducing gas may be, for example, a hydrogen-based gas such as hydrogen (H2) gas, a hydrogen-containing gas, activated hydrogen gas, etc. The activated hydrogen gas may be, for example, hydrogen gas activated by plasma.

[0073] It is preferable to use a hydrogen-containing gas as the first reducing gas. This allows the halogen element that inhibits the adsorption of the Group 14 element-containing gas to the film to be easily reduced and desorbed. Therefore, in steps D and F, the adsorption of the Group 14 element to the film is promoted, and the film formation speed can be improved.

[0074] [Step D] After step C is completed, a Group 14 element-containing gas is supplied from nozzle 249a to wafer 200 in processing chamber 201, i.e., to the surface of the film formed on wafer 200 and containing a Group 13 element or a Group 15 element as a main element, and an inert gas is supplied from each of nozzles 249b to 249e.

[0075] Specifically, the valve 243a is opened to allow a Group 14 element-containing gas to flow into the gas supply pipe 232a. The Group 14 element-containing gas is adjusted in flow rate by the MFC 241a, supplied into the processing chamber 201 through the nozzle 249a, and exhausted from the exhaust port 231a. At this time, the valves 243g to 243j are opened to supply an inert gas into the processing chamber 201 through each of the nozzles 249b to 249e.

[0076] By supplying a Group 14 element-containing gas to the wafer 200 from the nozzle 249a under processing conditions described below, a film containing a Group 14 element as a main element can be formed on the surface of the wafer 200, i.e., on the film formed on the wafer 200 and containing a Group 13 element or a Group 15 element as a main element.

[0077] As the group 14 element-containing gas, those mentioned above for step A can be used.

[0078] The processing conditions in step B are as follows: Dopant gas supply flow rate: 10 to 400 sccm Dopant gas supply time: 1 to 30 minutes Inert gas supply flow rate (per gas supply pipe): 300~5000sccm Processing temperature (second temperature): 350~550℃ Processing pressure: 0.1~1000Pa Examples are given below.

[0079] The processing conditions in step C are as follows: First reduction gas supply flow rate: 10 to 3000 sccm First reduction gas supply time: 1 to 30 minutes The other processing conditions are the same as those in step B.

[0080] The processing conditions in step D are as follows: Flow rate of Group 14 element-containing gas: 10 to 3000 sccm Group 14 element-containing gas supply time: 0.1 to 30 minutes The other processing conditions are the same as those in step B.

[0081] [Step F] After step E is completed, a Group 14 element-containing gas is supplied from nozzle 249a to wafer 200 in processing chamber 201, i.e., to the surface of the film formed on wafer 200 and containing a Group 14 element as a main element, and an inert gas is supplied from each of nozzles 249b to 249e.

[0082] Specifically, the valve 243a is opened to allow a Group 14 element-containing gas to flow into the gas supply pipe 232a. The Group 14 element-containing gas is adjusted in flow rate by the MFC 241a, supplied into the processing chamber 201 through the nozzle 249a, and exhausted from the exhaust port 231a. At this time, the valves 243g to 243j are opened to supply an inert gas into the processing chamber 201 through each of the nozzles 249b to 249e.

[0083] By supplying a Group 14 element-containing gas to the wafer 200 from the nozzle 249a under processing conditions described below, it is possible to form a film containing a Group 14 element as a main element on the surface of the wafer 200, i.e., on the film containing a Group 14 element as a main element formed on the wafer 200.

[0084] As the group 14 element-containing gas, those mentioned above for step A can be used.

[0085] The processing conditions in step F are as follows: Flow rate of Group 14 element-containing gas: 10 to 5000 sccm Group 14 element-containing gas supply time: 1 to 30 minutes Inert gas supply flow rate (per gas supply pipe): 300~3000sccm Processing temperature (second temperature): 350~550℃ Processing pressure: 0.1~1000Pa The other processing conditions are the same as those in step B.

[0086] (After purging and atmospheric pressure recovery) After the Si film formation step is completed, N2 gas is supplied as a purge gas from each of the nozzles 249a to 249c into the processing chamber 201 and exhausted from the exhaust port 231a. This purges the processing chamber 201, and gas and reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (after-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (return to atmospheric pressure).

[0087] (Boat unloading and wafer discharging) The seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafers 200 are carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the boat 217 (boat unloading). 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 being carried out to the outside of the reaction tube 203, the processed wafers 200 are taken out of the boat 217 (wafer discharge).

[0088] (3) Effects of this mode According to this aspect, one or more of the following effects can be obtained.

[0089] (a) In the film formation step, a film containing a Group 14 element as a main element is formed on a seed layer in step A. This makes it possible to suppress an increase in surface roughness when a film containing a halide of a Group 13 element or a Group 15 element as a main component is formed in step B.

[0090] (b) In step C, the halogen element of the film containing a halide of a Group 13 element or a Group 15 element as a main component can be reduced and removed to form a film containing a Group 13 element or a Group 15 element as a main element. Therefore, in step D, the adsorption of the Group 14 element-containing gas to the film can be prevented from being hindered by the halogen element.

[0091] (c) By providing a film containing a Group 14 element as a main element as a Cap layer on the film containing a Group 13 element or a Group 15 element as a main element in step D, it is possible to suppress the loss of the dopant (i.e., the Group 13 element or the Group 15 element) from the film.

[0092] (d) Furthermore, by providing a film containing a Group 14 element as a main element as a Cap layer on a film containing a Group 13 element or a Group 15 element as a main element in step D, it is possible to suppress an increase in surface roughness due to loss of dopants from the film.

[0093] (e) By performing a cycle including steps B to D in this order a predetermined number of times in step E, it is possible to form a film that is doped with a group 13 element or a group 15 element, contains a group 14 element as a main element, and has small surface roughness.

[0094] (f) In the film forming step, by further performing step F, the Cap layer of the film on the wafer 200 can be made thicker, and the loss of dopants from the film can be further suppressed.

[0095] (g) In the seed layer formation step, by forming a seed layer, the surface roughness of the film formed on the wafer 200 can be reduced.

[0096] (4) Variations The film forming steps in this embodiment are not limited to the embodiment shown in Figures 4 and 5, and can be modified as shown in the following modified examples. These modified examples can be combined as desired. Unless otherwise specified, the process procedure and process conditions in each step of each modified example can be the same as the process procedure and process conditions in each step of the substrate processing sequence described above.

[0097] (Variation 1) In the film formation sequence shown in FIG. 4 and FIG. 5, an example in which the seed layer forming step is performed has been described, but step G may not be performed.

[0098] (Variation 2) In the film formation sequence shown in FIGS. 4 and 5, an example in which step C, that is, the step of supplying the first reducing gas, is performed has been described, but step C may not be performed.

[0099] (Variation 3) In the film formation sequence shown in FIGS. 4 and 5, a dopant containing a halide of a Group 13 element or a Group 15 element is used in step B, but a dopant containing a non-halogen compound of a Group 13 element or a Group 15 element, for example, a hydride, may be used. As a dopant gas containing a hydride of a Group 13 element, a gas containing a Group 13 element that becomes a solid by itself (such as boron (B)) such as borane (BH3) or diborane (B2H6) gas can be used. In addition, as a dopant gas containing a hydride of a Group 15 element, a gas containing a Group 15 element that becomes a solid by itself (P, arsenic (As), etc.), such as phosphine (PH3, abbreviated as PH) gas or arsine (AsH3) gas, can be used. In the case of non-halogen compounds of Group 13 or Group 15 elements, the Group 15 elements selected in this disclosure do not include nitrogen (N).

[0100] (Variation 4) In the film formation sequence shown in FIGS. 4 and 5, an example in which step F is performed has been described, but step F may not be performed.

[0101] (Variation 5) In at least the last cycle in step E, the supply time of the Group 14 element-containing gas in step D may be set to be longer than the supply time of the Group 14 element-containing gas in step A. This makes it possible to reduce the film formation time in step A while thickening the Cap layer formed in step E, thereby suppressing the loss of dopants from the film on the wafer 200. In addition, in all cycles in step E, the supply time of the Group 14 element-containing gas in step D may be set to be longer than the supply time of the Group 14 element-containing gas in step A. This makes it possible to thicken all the films formed in step D, thereby further suppressing the loss of dopants from the films on the wafer 200.

[0102] The supply time of the Group 14 element-containing gas in step D may be, for example, 1 to 10 times the supply time of the Group 14 element-containing gas in step A.

[0103] (Variation 6) 4 and 5, an example in which steps G1 and G2 are performed once each in this order in step G has been described, but steps G1 and G2 may be alternately performed, that is, a cycle of performing steps G1 and G2 asynchronously and non-simultaneously may be performed a predetermined number of times (m times, m is an integer of 1 or more). This makes it possible to form a seed layer on the wafer 200 in which the above-mentioned nuclei are formed at a high density.

[0104] (Variation 7) In the film forming sequence shown in FIGS. 4 and 5, an example in which step G2 is performed in step G has been described, but step G2 may not be performed.

[0105] (Variation 8) 4 and 5, an example in which the second halosilane-based gas is supplied in step G2 of step G has been described, but a second reducing gas may be supplied instead of the second halosilane-based gas. When the second reducing gas is supplied instead of the second halosilane-based gas, step G2 may be performed in the same process as when the second halosilane-based gas is used.

[0106] Examples of the second reducing gas include hydrogen (H2) gas, monosilane (SiH4, abbreviated as MS) gas, disilane (Si2H6, abbreviated as DS) gas, trisilane (Si3H8) gas, and tetrasilane (Si4H 10 ) gas, pentasilane (SiH 12 ) gas, hexasilane (Si6H 14 A silicon hydride gas such as a fluorine-containing gas can be used as the second reducing gas. The second reducing gas may contain a silicon element. By using the second reducing gas, the surface roughness of the film formed on the wafer 200 can be reduced.

[0107] When the second reducing gas contains Si element, it is possible to form seeds (nuclei) by adsorbing Si contained in the second reducing gas to the surface of the wafer 200 cleaned in step G1. Also, the H element contained in the second reducing gas can reduce and remove the halogen element derived from the first halosilane gas on the surface of the wafer 200 cleaned in step G1. This can reduce the surface roughness of the film formed on the wafer 200.

[0108] (Variation 9) In the film formation step, a film may be formed on the wafer 200, for example, by the film formation sequence shown below.

[0109] MS → (BCl3 → H2 → MS) × n MS → (BCl3 → H2 → MS) × n → MS

[0110] (Variation 10) In the seed layer formation step, ie, step G, a seed layer may be formed on the wafer 200, for example, by the film formation sequence shown below.

[0111] (MS→HCDS)×m (DCS→DS)×m (HCDS→H2)×m (HCDS → SiH4) × m (HCDS → Si2H6) × m

[0112] (Variation 11) The wafer 200 as a substrate may have a microstructure by previously performing microfabrication on the surface. For example, as shown in FIG. 6, a first recess D1 extending perpendicularly to the surface of the wafer 200 may be formed on the surface of the wafer 200. Also, for example, as shown in FIG. 6, a plurality of second recesses D2 may be formed that are connected perpendicularly to the longitudinal direction of the first recess D1 and extend in the in-plane direction of the wafer 200. The first recess D1 means a trench or a hole, and the second recess D2 means a space in which a floating gate formed in the trench or the hole is formed. In the film formation step of the present disclosure, a film is formed in the first recess D1 and the second recess D2. The film formation step of the present disclosure makes it possible to form a film with small surface roughness even when the wafer 200 has a microstructure. That is, it becomes possible to uniformly form a film in the first recess D1 and the second recess D2.

[0113] <Other aspects> Although the embodiments of the present disclosure have been specifically described above, the present disclosure is not limited to the above embodiments and can be modified in various ways without departing from the spirit and scope of the present disclosure.

[0114] In the above embodiment, the nozzles 249a to 249e are provided adjacent to each other (close to each other), but the present disclosure is not limited to such an embodiment. For example, the nozzles 249a, 249b, 249d, and 249c may be provided at positions away from the nozzle 249c in a space that is annular in plan view between the inner wall of the reaction tube 203 and the wafer 200.

[0115] In the above embodiment, the first to fifth supply units are configured by the nozzles 249a to 249e, and five nozzles are provided in the processing chamber 201. However, the present disclosure is not limited to such an embodiment. For example, at least any one of the first to fifth supply units may be configured by two or more nozzles. Furthermore, a nozzle other than the first to fifth supply units may be newly provided in the processing chamber 201, and an inert gas or various processing gases may be further supplied using this nozzle. When a nozzle other than the nozzles 249a to 249e is provided in the processing chamber 201, the newly provided nozzle may be provided at a position facing the exhaust port 231a in a plan view, or may be provided at a position not facing the exhaust port 231a. That is, the newly provided nozzle may be provided at a position away from the nozzles 249a-249e, for example, in the space between the inner wall of the reaction tube 203 and the wafer 200 that is annular in plan view, at an intermediate position between the nozzles 249a-249e and the exhaust port 231a along the outer periphery of the wafer 200, or at a position near that intermediate position.

[0116] It is preferable that recipes used for substrate processing are prepared individually according to the processing contents and stored in the storage device 121c via an electric communication line or an external storage device 123. Then, when starting processing, it is preferable that the CPU 121a appropriately selects an appropriate recipe from the multiple recipes stored in the storage device 121c according to the substrate processing contents. This makes it possible to form films of various film types, composition ratios, film qualities, and thicknesses with good reproducibility using a single substrate processing device. It also reduces the burden on the operator and makes it possible to start processing quickly while avoiding operational errors.

[0117] The above-mentioned recipes may not only be newly created, but may also be prepared by modifying an existing recipe that has already been installed in the substrate processing apparatus. When modifying a recipe, the modified recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium on which the recipe has been recorded. Also, an existing recipe that has already been installed in the substrate processing apparatus may be directly modified by operating the input / output device 122 provided in the existing substrate processing apparatus.

[0118] In the above-mentioned embodiment, 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 disclosure is not limited to the above-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a single-wafer type substrate processing apparatus that processes one or several substrates at a time. Also, in the above-mentioned embodiment, 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-mentioned embodiment, and can be suitably applied to, for example, a case where a film is formed using a substrate processing apparatus having a cold-wall type processing furnace.

[0119] When using these substrate processing apparatuses, film formation can be performed in the same sequence and under the same processing conditions as in the above-mentioned embodiments and modifications, and the same effects can be obtained.

[0120] The above-mentioned aspects and modifications may be used in combination as appropriate. The processing procedures and processing conditions in this case may be the same as those of the above-mentioned aspects.

[0121] The various effects described in this disclosure are obtained not only under conditions in which the process gas supplied to the substrate is thermally decomposed (conditions in which the self-limit is not applied), but also under conditions in which the process gas supplied to the substrate is not thermally decomposed (conditions in which the self-limit is applied), with the same tendency. However, among the various effects described above, the effect of adjusting the in-plane film thickness distribution is particularly effectively obtained when the film is formed on the substrate under conditions in which the process gas supplied to the substrate is thermally decomposed and a CVD reaction occurs.

[0122] <Preferred aspects of the present disclosure> Preferred aspects of the present disclosure will be described below.

[0123] (Appendix 1) According to one aspect of the present disclosure, (a) supplying a Group 14 element-containing gas to a substrate; (e) performing a cycle including, in this order, a predetermined number of cycles after (a), the cycles including (b) supplying to the substrate a dopant gas containing a halide of a Group 13 element or a Group 15 element, (c) supplying to the substrate a first reducing gas, and (d) supplying to the substrate a Group 14 element-containing gas; A method for manufacturing a semiconductor device having the above structure is provided.

[0124] (Appendix 2) 2. The method according to claim 1, comprising: In at least the last cycle in (e), the supplying time in (d) is longer than the supplying time in (a).

[0125] (Appendix 3) 3. The method according to claim 2, comprising: In all of the cycles in (e), the supplying time in (d) is longer than the supplying time in (a).

[0126] (Appendix 4) The method according to any one of appendix 1 to 3, (f) after (e), supplying the Group 14 element-containing gas to the substrate.

[0127] (Appendix 5) The method according to any one of appendix 1 to 4, (g) before (a), supplying a halosilane-based gas to the substrate.

[0128] (Appendix 6) 6. The method according to claim 5, In (g), two types of the halosilane-based gases are supplied.

[0129] (Appendix 7) 6. The method according to claim 5, In (g), after the halosilane-based gas is supplied, a second reducing gas is supplied.

[0130] (Appendix 8) 8. The method according to claim 7, The second reducing gas contains elemental Si.

[0131] (Appendix 9) The method according to any one of appendix 1 to 8, 9. The method for manufacturing a semiconductor device according to claim 1, wherein the Group 14 element-containing gas is any one of SiH4 gas, Si2H6 gas, Si3H8 gas, GeH4 gas, Ge2H6 gas, and Ge3H8 gas.

[0132] (Appendix 10) The method according to any one of appendix 1 to 9, The dopant gas contains a B element.

[0133] (Appendix 11) 11. The method of claim 10, further comprising: The dopant gas contains Cl element.

[0134] (Appendix 12) The method according to any one of claims 1 to 11, The first reducing gas is a hydrogen-containing gas.

[0135] (Appendix 13) The method according to any one of claims 1 to 12, A first recess is formed in the surface of the substrate, the first recess extending in an in-plane direction of the substrate.

[0136] (Appendix 14) 14. The method of claim 13, comprising: A plurality of second recesses are formed on the surface of the substrate, the second recesses being connected perpendicularly to the longitudinal direction of the first recesses and extending in an in-plane direction of the substrate.

[0137] (Appendix 15) According to another aspect of the present disclosure, (a) supplying a Group 14 element-containing gas to a substrate; (e) performing a cycle including, in this order, (b) a step of supplying a gas containing a Group 13 element or a Group 15 element to the substrate, and (d) a step of supplying a gas containing a Group 14 element to the substrate a predetermined number of times after (a); A method for manufacturing a semiconductor device having the above structure is provided.

[0138] (Appendix 16) According to another aspect of the present disclosure, a processing chamber in which the substrate is processed; a first supply system that supplies a Group 14 element-containing gas from a first supply unit to the substrate in the processing chamber; a second supply system that supplies a dopant gas containing a halide of a Group 13 element or a Group 15 element to the substrate in the processing chamber from a second supply unit; a third supply system that supplies a first reducing gas from a third supply unit to the substrate in the processing chamber; In the processing chamber, (a) supplying the Group 14 element-containing gas to the substrate; (e) performing a cycle including, in this order, (b) a process of supplying to the substrate a dopant gas containing a halide of the Group 13 element or the Group 15 element, (c) a process of supplying to the substrate the first reducing gas, and (d) a process of supplying to the substrate a gas containing the Group 14 element, a predetermined number of times after (a); a control unit configured to be able to control the first supply system, the second supply system, and the third supply system so as to perform A substrate processing apparatus having a

[0139] (Appendix 17) According to another aspect of the present disclosure, There is provided a program for causing a substrate processing apparatus to execute each procedure (each step) in appendix 1 by a computer, or a computer-readable recording medium having the program recorded thereon.

Claims

1. (a) supplying a Group 14 element-containing gas to a substrate; (e) performing a cycle including, in this order, a predetermined number of cycles after (a), the cycles including (b) supplying to the substrate a dopant gas containing a halide of a Group 13 element or a Group 15 element, (c) supplying to the substrate a first reducing gas, and (d) supplying to the substrate a Group 14 element-containing gas; having A substrate processing method, wherein in at least the last cycle in (e), the supplying time in (d) is longer than the supplying time in (a).

2. 2. The substrate processing method according to claim 1, wherein in all the cycles of (e), the supplying time in (d) is longer than the supplying time in (a). (a) supplying a Group 14 element-containing gas to a substrate; (e) performing a cycle including, in this order, a predetermined number of cycles after (a), the cycles including (b) supplying to the substrate a dopant gas containing a halide of a Group 13 element or a Group 15 element, (c) supplying to the substrate a first reducing gas, and (d) supplying to the substrate a Group 14 element-containing gas; (f) after (e), supplying the Group 14 element-containing gas to the substrate; A substrate processing method comprising the steps of:

4. 4. The substrate processing method according to claim 1, further comprising: (g) a step of supplying a halosilane-based gas to the substrate before (a).

5. 5. The substrate processing method according to claim 4, wherein in (g), two types of the halosilane-based gases are supplied.

6. 5. The substrate processing method according to claim 4, wherein in (g), a second reducing gas is supplied after the supply of the halosilane-based gas.

7. The substrate processing method according to claim 6 , wherein the second reducing gas contains an Si element.

8. The Group 14 element-containing gas is SiH ４ Gas, Si ２ H ６ Gas, Si ３ H ８ Gas, GeH ４ Gas, Ge ２ H ６ Gas or Ge ３ H ８ 8. The substrate processing method according to claim 1, wherein the gas is any one of the gases.

9. 9. The substrate processing method according to claim 1, wherein the dopant gas contains a B element.

10. The substrate processing method according to claim 9 , wherein the dopant gas contains Cl element.

11. 11. The substrate processing method according to claim 1, wherein the first reducing gas is a hydrogen-containing gas.

12. The substrate processing method according to any one of claims 1 to 11, wherein a first recess is formed in the surface of the substrate, the first recess extending in an in-plane direction of the substrate.

13. The substrate processing method according to claim 12 , wherein a plurality of second recesses are formed in the surface of the substrate, the second recesses being connected perpendicular to the longitudinal direction of the first recesses and extending in an in-plane direction of the substrate.

14. a first supply system that supplies a Group 14 element-containing gas to the substrate from a first supply unit; a second supply system that supplies a dopant gas containing a halide of a Group 13 element or a Group 15 element to the substrate from a second supply unit; a third supply system that supplies a first reducing gas to the substrate from a third supply unit; (a) supplying the Group 14 element-containing gas to the substrate; (e) performing a cycle including, in this order, (b) a process of supplying to the substrate a dopant gas containing a halide of the Group 13 element or the Group 15 element, (c) a process of supplying to the substrate the first reducing gas, and (d) a process of supplying to the substrate a gas containing the Group 14 element, a predetermined number of times after (a); (e) in at least the last cycle, the supplying time in (d) is longer than the supplying time in (a); a control unit configured to be able to control the first supply system, the second supply system, and the third supply system so as to perform A substrate processing apparatus comprising:

15. (a) supplying a Group 14 element-containing gas to a substrate; (e) performing a cycle including, in this order, a predetermined number of cycles after (a): (b) supplying to the substrate a dopant gas containing a halide of a Group 13 element or a Group 15 element; (c) supplying to the substrate a first reducing gas; and (d) supplying to the substrate a Group 14 element-containing gas; (e) at least in the last cycle, the duration of the supply in (d) is longer than the duration of the supply in (a); A program for causing a computer to execute the above in a substrate processing apparatus.

16. (a) supplying a Group 14 element-containing gas to a substrate; (e) performing a cycle including, in this order, a predetermined number of cycles after (a), the cycles including (b) supplying to the substrate a dopant gas containing a halide of a Group 13 element or a Group 15 element, (c) supplying to the substrate a first reducing gas, and (d) supplying to the substrate a Group 14 element-containing gas; having A method for manufacturing a semiconductor device, comprising the steps of: (e) supplying a time period during which the supply is performed in (d) is longer than a time period during which the supply is performed in (a).

17. A first supply system that supplies a Group 14 element-containing gas to a substrate from a first supply unit; a second supply system that supplies a dopant gas containing a halide of a Group 13 element or a Group 15 element to the substrate from a second supply unit; a third supply system that supplies a first reducing gas to the substrate from a third supply unit; (a) supplying the Group 14 element-containing gas to the substrate; (e) performing a cycle including, in this order, (b) a process of supplying to the substrate a dopant gas containing a halide of the Group 13 element or the Group 15 element, (c) a process of supplying to the substrate the first reducing gas, and (d) a process of supplying to the substrate a gas containing the Group 14 element, a predetermined number of times after (a); (f) after (e), supplying the Group 14 element-containing gas to the substrate; a control unit configured to be able to control the first supply system, the second supply system, and the third supply system so as to perform A substrate processing apparatus comprising: (a) supplying a Group 14 element-containing gas to a substrate; (e) performing a cycle including, in this order, a predetermined number of cycles after (a): (b) supplying to the substrate a dopant gas containing a halide of a Group 13 element or a Group 15 element; (c) supplying to the substrate a first reducing gas; and (d) supplying to the substrate a Group 14 element-containing gas; (f) after (e), supplying the Group 14 element-containing gas to the substrate; and performing a cycle including the steps in this order a predetermined number of times after (a). A program for causing a computer to execute the above in a substrate processing apparatus.

19. (a) supplying a Group 14 element-containing gas to a substrate; (e) performing a cycle including, in this order, a predetermined number of cycles after (a), the cycles including (b) supplying to the substrate a dopant gas containing a halide of a Group 13 element or a Group 15 element, (c) supplying to the substrate a first reducing gas, and (d) supplying to the substrate a Group 14 element-containing gas; (f) after (e), supplying the Group 14 element-containing gas to the substrate; A method for manufacturing a semiconductor device having the above structure.

Images