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

Abstract

Provided is a technique that contributes to the miniaturization of a semiconductor device. Comprises: (a) a step for supplying a first gas containing a first Group 14 element to a substrate; (b) a step for supplying a second gas containing a second Group 14 element to the substrate; (c) a step of supplying a modifying gas to the substrate; (d) forming a film containing the first group 14 element by performing (a) n times (n is an integer of 1 or 2 or more), and then forming a film containing at least the second group 14 element by performing (b) and (c) at least m times (m is an integer of 1 or 2 or more); and (e) a step for forming a film containing at least the first Group 14 element by performing (a) and (c) at least once (l is an integer of 1 or 2 or more) after (d).

Description

Technical Field

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

[0002] In the process of manufacturing semiconductor devices (equipment) such as LSI, a film forming process of forming a film containing a Group 14 element on a substrate is sometimes performed (for example, Patent Documents 1 and 2).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2014-84506

[0006] Patent Document 2: Japanese Patent Application Publication No. 2017-224693 Summary of the invention

[0007] Problems to be solved by the invention

[0008] However, in recent years, there is an increasing demand for miniaturization of semiconductor devices (e.g., 3D NAND memory), and as a requirement for miniaturization, for example, a film containing a Group 14 element can be formed thinly, flatly, and uniformly even on a substrate having fine convex and concave portions on its surface.

[0009] Here, the present disclosure provides a technology that contributes to miniaturization of semiconductor devices.

[0010] Methods for solving problems

[0011] According to one embodiment of the present disclosure, a technology is provided to perform the following steps:

[0012] (a) supplying a first gas containing a first Group 14 element to a substrate;

[0013] (b) supplying a second gas containing a second Group 14 element to the substrate;

[0014] (c) supplying a modified gas to the substrate;

[0015] (d) a step of performing (a) n times (n is an integer of 1 or 2 or more) to form a film containing the first Group 14 element, and then performing (b) and (c) at least m times (m is an integer of 1 or 2 or more) to form a film containing at least the second Group 14 element; and

[0016] (e) After (d), the step of performing (a) and (c) at least once (1 is an integer of 1 or 2) to form a film containing at least the first Group 14 element.

[0017] Effects of the Invention

[0018] According to the present disclosure, a technology that contributes to miniaturization of semiconductor devices can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] [ Figure 1 ] Figure 1 This is a schematic diagram of the structure of a substrate processing apparatus used in one embodiment, and shows a processing furnace portion in a longitudinal cross-sectional view.

[0020] [ Figure 2 ] Figure 2 A schematic diagram of a substrate processing device used in one embodiment is shown in FIG. Figure 1 The AA line cross-sectional view shows a diagram of a processing furnace portion.

[0021] [ Figure 3 ] Figure 3 This is a schematic diagram of the configuration of a controller of a substrate processing apparatus used in one embodiment, and is a diagram showing a control system of the controller in the form of a block diagram.

[0022] [ Figure 4 ] Figure 4 A diagram showing a film forming sequence according to one embodiment.

[0023] [ Figure 5 ] Figure 5 A diagram showing the film forming sequence of Modification Example 1.

[0024] [ Figure 6 ] Figure 6 A diagram showing the film forming sequence of Modification Example 2.

[0025] [ Figure 7 ] Figure 7 A diagram showing the film forming sequence of Modification Example 3.

[0026] [ Figure 8 ] Figure 8 A diagram showing the film forming sequence of Modification Example 4.

[0027] [ Fig. 9 ] Fig. 9 A diagram showing the film forming sequence of Modification Example 5.

[0028] [ Fig.10 ] Fig.10 A diagram showing the film forming sequence of Modification Example 6.

[0029] [ Fig.11 ] Fig.11 A diagram showing the film forming sequence of Modification Example 7.

[0030] [ Fig.12 ] Fig.12 A diagram showing the film forming sequence of Modification Example 8. DETAILED DESCRIPTION

[0031] An embodiment of the present disclosure is described below.

[0032] In addition, the drawings used in the following description are schematic diagrams, and the dimensional relationship of each element, the ratio of each element, etc. shown in the drawings do not necessarily have to be consistent with reality. In addition, the dimensional relationship of each element, the ratio of each element, etc. between multiple drawings do not have to be the same. In addition, the numerical range represented by "~" means that the range includes the numerical values ​​recorded before and after "~" as the lower limit and upper limit.

[0033] <One embodiment of the present disclosure>

[0034] [Configuration of substrate processing apparatus]

[0035] The substrate processing apparatus according to the present embodiment is a batch hot wall type apparatus (hereinafter referred to as substrate processing apparatus) configured to form a film on a wafer.

[0036] (Construction of treatment furnace)

[0037] like Figure 1 As shown, the processing furnace 202 included in the substrate processing apparatus 10 has a heater 207 as a heating device (heating mechanism, heating system). The heater 207 has a cylindrical shape and is supported by a heater base.

[0038] A reaction tube 203 constituting a reaction container (processing container) is disposed concentrically with the heater 207 on the inner side of the heater 207. The reaction tube 203 is made of a heat-resistant material (e.g., quartz (SiO2), silicon carbide (SiC), etc.) and has a cylindrical shape with a closed upper end and an open lower end. A manifold 209 (hereinafter referred to as MF209) is disposed below the reaction tube 203.

[0039] MF209 is made of metal such as stainless steel (SUS) and has a cylindrical shape with both the upper and lower ends being open. An O-ring 220 is provided as a sealing member between the upper end of MF209 and the reaction tube 203. A processing chamber 201 for processing a substrate is formed in the hollow portion of the processing container.

[0040] The processing chamber 201 is configured to accommodate wafers 200 as substrates in a horizontal position and arranged in multiple layers in a vertical direction using a wafer cassette 217 .

[0041] Nozzles 410, 420, 430 are provided in the processing chamber 201 to penetrate the side wall of the MF 209. The nozzles 410, 420, 430 are connected to the gas supply pipes 310, 320, 330, respectively.

[0042] In the gas supply pipes 310, 320, 330, mass flow controllers (MFCs) 312, 322, 332 as flow controllers (flow control units) and valves 314, 324, 334 as on-off valves are provided in order from the upstream side. Gas supply pipes 510, 520, 530 for supplying inert gas are connected to the downstream sides of the valves 314, 324, 334 of the gas supply pipes 310, 320, 330, respectively. In the gas supply pipes 510, 520, 530, MFCs 512, 522, 532 as flow controllers (flow control units) and valves 514, 524, 534 as on-off valves are provided in order from the upstream side, respectively.

[0043] like Figure 2 As shown, the nozzles 410, 420, 430 are configured as L-shaped nozzles, and the horizontal portions thereof are arranged to penetrate the side wall of the MF 209. The vertical portions of the nozzles 410, 420, 430 are arranged in a manner that they stand upright (above the arrangement direction of the wafers 200) along the inner wall of the reaction tube 203 in the annular space formed between the inner wall of the reaction tube 203 and the wafers 200 (i.e., they stand upright from one end side of the wafer arrangement area to the other end side). That is, the nozzles 410, 420, 430 are arranged 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.

[0044] Gas supply ports 410a, 420a, 430a for supplying gas are provided on the side surfaces of the nozzles 410, 420, 430 in a manner along the arrangement direction of the wafers 200 and corresponding to the substrate arrangement area where the wafers 200 are arranged. The gas supply ports 410a, 420a, 430a are opened toward the center direction of the reaction tube 203. A plurality of the gas supply ports 410a, 420a, 430a are provided from the bottom to the top of the reaction tube 203, and each of them has the same opening area and is further provided with the same opening spacing. However, the gas supply ports 410a, 420a, 430a are not limited to the above-mentioned form. For example, the gas supply ports 410a, 420a, 430a may be provided so that the opening area gradually increases from the bottom to the top of the reaction tube 203. Thus, the gas flow rate supplied from the gas supply ports 410a, 420a, 430a can be made uniform.

[0045] (Gas supply system) - First gas supply system -

[0046] A first gas containing a first Group 14 element (hereinafter referred to as the first element) is supplied from a gas supply pipe 310 to the processing chamber 201 via MFC 312, a valve 314, and a nozzle 410. In addition, an inert gas supply line for supplying an inert gas such as nitrogen is connected in parallel to the gas supply pipe 310, and is supplied to the processing chamber 201 via MFC 512, a valve 514, and a nozzle 410. The first gas supply system is mainly composed of the gas supply pipe 310, the MFC 512, and the valve 514.

[0047] - Second gas supply system -

[0048] A second gas containing a second Group 14 element (hereinafter referred to as the second element) is supplied from the gas supply pipe 320 to the processing chamber 201 via the MFC 322, the valve 324, and the nozzle 420. In addition, a gas supply line for supplying an inert gas such as nitrogen or a carrier gas such as hydrogen is connected in parallel to the gas supply pipe 320, and is supplied to the processing chamber 201 via the MFC 522, the valve 524, and the nozzle 420. The second gas supply system is mainly composed of the gas supply pipe 320, the MFC 522, and the valve 524.

[0049] - Reforming gas supply system -

[0050] The modified gas is supplied to the processing chamber 201 from the gas supply pipe 330 via the MFC 332, the valve 334 and the nozzle 430. In addition, an inert gas supply line for supplying an inert gas such as nitrogen is connected in parallel to the gas supply pipe 320, and is supplied to the processing chamber 201 via the MFC 532, the valve 534 and the nozzle 430. The modified gas supply system is mainly composed of the gas supply pipe 330, the MFC 532 and the valve 534.

[0051] (Gas Exhaust System)

[0052] One end of an exhaust pipe 231 is connected to the wall surface of MF209 as an exhaust flow path for exhausting the atmosphere of the processing chamber 201. The exhaust pipe 231 is installed with: a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure of the processing chamber 201, and an APC (Auto Pressure Controller, automatic pressure control) valve 243 as an exhaust valve (pressure adjustment unit), and a vacuum pump 246 as an exhaust device is installed at the end of the exhaust pipe 231. The gas exhaust system is mainly composed of the exhaust pipe 231, the pressure sensor 245 and the APC valve 243. The vacuum pump 246 can also be included in the gas exhaust system.

[0053] The APC valve 243 is a valve that can be opened and closed when the vacuum pump 246 is in operation, thereby exhausting and stopping the processing chamber 201. Furthermore, when the vacuum pump 246 is in operation, the valve opening is adjusted based on the pressure information detected by the pressure sensor 245, thereby forming a valve that can adjust the pressure of the processing chamber 201. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 243 and the pressure sensor 245. The vacuum pump 246 can also be considered to be included in the exhaust system. The exhaust pipe 231 is not limited to the case where it is set in the MF209, and can also be set in the reaction tube 203.

[0054] A sealing cap 219 (hereinafter referred to as the cap body 219) is provided below MF209 as a furnace cap body that can airtightly close the lower end opening of MF209. The cap body 219 is formed of a metal such as SUS and is disc-shaped. An O-ring 220 is provided on the top of the cap body 219 as a sealing member that abuts against the lower end of MF209. A rotating mechanism 267 for rotating the wafer box 217 described later is provided on the opposite side of the processing chamber 201 relative to the cap body 219. The rotating shaft 255 of the rotating mechanism 267 passes through the cap body 219 and is connected to the wafer box 217.

[0055] The cap body 219 is configured to be raised and lowered in the vertical direction by a wafer box elevator 115 (hereinafter referred to as the elevator 115) as a lifting mechanism vertically arranged outside the reaction tube 203. The elevator 115 is configured to move the wafer box 217 into and out of the processing chamber 201 by raising and lowering the cap body 219. The elevator 115 is configured as a transport device that transports the wafer box 217 into and out of the processing chamber 201.

[0056] (Wafer Box)

[0057] The wafer box 217 as a substrate support is configured to support multiple (e.g., 25 to 200) wafers 200 in a horizontal posture and in a vertical direction in multiple stages, that is, arranged at intervals. A top plate 215 is provided on the top plate portion of the wafer box 217. The wafer box 217 and the top plate 215 are made of, for example, a heat-resistant material such as quartz or SiC. In the heat-insulating area as the lower part of the wafer box 217, a heat-insulating plate 218 made of a heat-resistant material is supported in multiple stages in a horizontal posture.

[0058] (Heater)

[0059] In the processing chamber 201, as Figure 2As shown, a temperature sensor 263 is provided as a temperature detector. The power supply to the heater 207 is adjusted based on the temperature information detected by the temperature sensor 263, so that the temperature in the processing chamber 201 becomes a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203 in the same manner as the nozzles 410, 420, 430.

[0060] (Controller)

[0061] like Figure 3 As shown, the controller 121 as a control unit (control unit) is configured as a computer having a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I / O interface 121d. RAM121b, a storage device 121c, and an I / O interface 121d are configured to exchange data with the CPU121a via an internal bus. The controller 121 is connected to an input / output device 122 configured as, for example, a touch panel. In addition, the substrate processing device may also be configured to have one control unit or multiple control units. That is, the control for performing the sequence described later may be implemented using one control unit or multiple control units. In addition, multiple control units may be configured as a control system interconnected via a wired or wireless communication network, or the control system as a whole may execute the control for performing the sequence described later. In this specification, when the term "control unit" is used, it includes not only one control unit but also a plurality of control units and a control system composed of a plurality of control units.

[0062] The storage device 121c is composed of, for example, a flash memory, a HDD (Hard Disk Drive), an SSD (Solid State Drive), etc. In the storage device 121c, at least one of a control program for controlling the action of the substrate processing device, a process recipe (also called a recipe) recording each program (each process, each step) and conditions of the semiconductor processing method and the manufacturing method of the semiconductor device (equipment), etc. is stored in a readable form. The recipe is combined in a manner that each program is implemented using the controller 121 and a predetermined result can be obtained, and functions as a program. Hereinafter, the recipe, control program, etc. are also simply referred to as a program. In this specification, when the term "program" is used, there are situations where only the recipe is included alone, only the control program is included alone, or a combination of the recipe and the control program is included. RAM121b is configured as a storage area for temporarily storing programs, data, etc. read by CPU121a.

[0063] The I / O interface 121d is connected to at least any one of the MFCs 312, 322, 332, 512, 522, 532, valves 314, 324, 334, 514, 524, 534, pressure sensor 245, APC valve 243, vacuum pump 246, heater 207, temperature sensor 263, rotating mechanism 267, elevator 115, and the like.

[0064] The CPU 121a is configured to read out a control program from the storage device 121c and execute it, and to read out a recipe from the storage device 121c according to an input of an operation command from the input / output device 122. The CPU 121a is configured to control, according to the contents of the read-out recipe, the flow rate adjustment operation of various gases by the MFCs 312, 322, 332, 512, 522, 532, the opening and closing operation of the valves 314, 324, 334, 514, 524, 534, the opening and closing operation of the APC valve 243, the pressure adjustment operation of the APC valve 243 based on the pressure sensor 245, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the start and stop of the vacuum pump 246, the rotation and rotation speed adjustment operation of the wafer cassette 217 by the rotation mechanism 267, the lifting and lowering operation of the wafer cassette 217 by the lifter 115, and the like.

[0065] The controller 121 can be constructed by installing the above-mentioned program stored in an external storage device (for example: a magnetic disk such as a hard disk; an optical disk such as a CD, a DVD; a semiconductor memory such as a USB memory, a memory card, etc.) 123 on a computer. The storage device 121c and the external storage device 123 are configured as a computer-readable recording medium. Hereinafter, they are also simply collectively referred to as recording media. In this specification, the recording medium may include only the storage device 121c alone, only the external storage device 123 alone, or both. It should be noted that providing a program to a computer may also be done without using an external storage device 123, but by using communication means such as the Internet and a dedicated line.

[0066] [Substrate processing steps]

[0067] Next, using the substrate processing apparatus 10 described above, as one step of the manufacturing process of the apparatus according to the present embodiment (ie, a substrate processing method), Figure 4 An example of a method of manufacturing the apparatus by forming a film on a wafer 200 as a substrate will be described. In the following description, the operation of each unit constituting the substrate processing apparatus 10 is controlled by the controller 121 .

[0068] exist Figure 4 In the film formation sequence shown, carry out:

[0069] (a) step Si(a) of supplying a first gas containing a first element to the wafer 200; (b) step Ge(b) of supplying a second gas containing a second element to the wafer 200 substrate; and (c) step R(c) of supplying a modified gas to the wafer 200. Figure 4 In the process, the following steps are performed: using steps Si(a), Ge(b) and R(c), after performing step Si(a) n times (n is an integer greater than or equal to 1 or 2) to form a film containing the first element (hereinafter also referred to as "first element film A"), step (d) is performed to form a film containing the second element (hereinafter also referred to as "second element film B") on the wafer 200 by performing step Ge(b) and step R(c) m times (m is an integer greater than or equal to 1 or 2); and (e) after step (d), performing step Si(a) and step R(c) l times (l is an integer greater than or equal to 1 or 2) to form a film containing the first element (hereinafter also referred to as "first element film C") on the wafer 200. Here, in step (e), step Si(a) performed first is referred to as "step Si(a1)".

[0070] Figure 4 In step (d), step R(c) is performed after step Ge(b). In step (e), step R(c) is performed after step Si(a).

[0071] In this specification, the above-mentioned processing sequence may be expressed as follows for convenience. The same expression is also used in the description of other aspects, modified examples, etc.

[0072] (d){[Si(a1)×n]→[(Ge(b)→R(c))×n]}→(e)[(Si(a)→R(c))×n]

[0073] In addition, when the term "wafer" is used in this specification, it may mean "the wafer itself" or "a stack (aggregate) of a wafer and predetermined layers, films, etc. formed on its surface" (that is, the predetermined layers, films, etc. formed on the surface are all referred to as wafers). In addition, when the term "wafer surface" is used in this specification, it may mean "the surface (exposed surface) of the wafer itself" or "the surface of the predetermined layers, films, etc. formed on the wafer, that is, the outermost surface of the wafer as a stack)". When the term "substrate" is used in this specification, it has the same meaning as when the term "wafer" is used.

[0074] Hereinafter, each step of the substrate processing method according to the present embodiment will be described.

[0075] (Substrate transfer)

[0076] The plurality of wafers 200 are loaded into the processing chamber 201. Specifically, when the plurality of wafers 200 are loaded into the wafer box 217, as shown in FIG. Figure 1 As shown, the wafer cassette 217 supporting a plurality of wafers 200 is lifted by the wafer cassette elevator 115 and carried into the processing chamber 201. In this state, the sealing cap 219 seals the lower end opening of the MF 209 via the O-ring 220.

[0077] (Pressure adjustment and temperature adjustment)

[0078] The vacuum pump 246 performs vacuum exhaust so that the pressure in the processing chamber 201 is the desired one. At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 243 is controlled (pressure adjustment) based on the measured pressure information. In addition, the heater 207 performs heating so that the processing chamber 201 reaches the desired temperature. At this time, the amount of power supplied to the heater 207 is controlled (temperature adjustment) based on the temperature information detected by the temperature sensor 263 so that the desired temperature distribution is achieved in the processing chamber 201. The heating in the processing chamber 201 by the heater 207 is continued at least until the processing of the wafer 200 is completed.

[0079] Furthermore, the wafer cassette 217 and the wafer 200 are rotated by the rotation mechanism 267. The rotation of the wafer cassette 217 and the wafer 200 by the rotation mechanism 267 is continued at least until the processing of the wafer 200 is completed.

[0080] (Film Forming)

[0081] Secondly, according to Figure 4 The films were formed in the order shown.

[0082] - Step (d) -

[0083] In step (d), first, step Si(a1)n times (n is an integer greater than 1 or 2) are performed. In step Si(a1), a first gas containing a first element is supplied to the wafer 200 in the processing chamber 201. Specifically, valve 314 is opened to circulate the first gas into the gas supply pipe 310. The first gas is flow-regulated by MFC312, supplied to the processing chamber 201 from the gas supply port 410a via the nozzle 410, and then exhausted from the exhaust pipe 231. At this time, the first gas is supplied to the wafer 200. In addition, valve 514 is opened at the same time to circulate an inactive gas into the gas supply pipe 310. The inactive gas is flow-regulated by MFC512, supplied to the processing chamber 201 together with the first gas, and then exhausted from the exhaust pipe 231. A first element film is formed by supplying the first gas containing the first element to the wafer 200.

[0084] After the formation of the first element film A is completed, the valve 314 is closed to stop the supply of the first gas. At this time, the APC valve 243 is kept open to exhaust the inside of the processing chamber 201, and the first gas remaining in the processing chamber 201 is removed from the processing chamber 201. In addition, the valve 514 is kept open to maintain the supply of the inert gas to the processing chamber 201. The inert gas acts as a purge gas.

[0085] In step (d), step Si(a1) performs the above operation n times (n is an integer greater than 1 or 2).

[0086] In step (d), the first element film A is formed by step Si(a1). Here, in step Si(a1), it is preferred that a Si seed layer is formed as the first element film A.

[0087] As the processing conditions of step (a1) in step (d), the following can be exemplified: first gas supply flow rate: 10 to 1000 sccm, first gas supply time: 0.1 to 30 minutes, inert gas supply flow rate: 10 to 3000 sccm, processing temperature: 250 to 650° C., and processing pressure: 1 to 1000 Pa. Here, the processing temperature refers to the temperature of the wafer 200 or the temperature in the processing chamber 201. The processing pressure refers to the pressure in the processing chamber 201. The gas supply time refers to the time for which the gas is continuously supplied. These are also the same in the following description.

[0088] In step (d), the number of cycles of step Si(a1) is, for example, 1 to 300 times, preferably 1 time.

[0089] Here, the first gas preferably contains Si as the first element. Examples of the Si-containing gas include disilane (Si2H6) gas, monosilane (SiH4) gas, trisilane (Si3H8) gas, tetrasilane (Si4H 10 ) gas, pentasilane (Si5H 12 ) gas, hexasilane (Si6H 14 ) gas and other silicon hydride gases.

[0090] In step (d), step Ge(b) and step R(c) are then performed m times (m is an integer greater than 1 or 2).

[0091] In step (d), step Ge(b) is performed first. Step Ge(b) is to supply a second gas containing a second Group 14 element (hereinafter referred to as the second element) to the wafer 200 in the processing chamber 201. Specifically, valve 324 is opened to circulate the second gas into the gas supply pipe 320. The second gas is flow-adjusted by MFC322, and then supplied to the processing chamber 201 from the gas supply port 420a via the nozzle 420, and then exhausted from the exhaust pipe 231. At this time, the second gas is supplied to the wafer 200. In addition, valve 524 is opened at the same time to circulate an inactive gas into the gas supply pipe 320. The inactive gas is flow-adjusted by MFC522, and then supplied to the processing chamber 201 together with the second gas, and then exhausted from the exhaust pipe 231. By supplying the first gas containing the second element to the wafer 200, a second element film before modification is formed.

[0092] After the formation of the second element film B is completed, the valve 324 is closed to stop the supply of the second gas. At this time, the processing chamber 201 is exhausted while the APC valve 243 is kept open, and the second gas remaining in the processing chamber 201 is removed from the processing chamber 201. In addition, the supply of the inactive gas to the processing chamber 201 is maintained while the valve 524 is kept open. The inactive gas acts as a purge gas.

[0093] In step (d), step R(c) is then performed. In step R(c), a modified gas is supplied to the wafer 200 in the processing chamber 201. Specifically, valve 334 is opened to circulate the modified gas into the gas supply pipe 330. The modified gas is flow-regulated by MFC332, and then supplied to the processing chamber 201 from the gas supply port 430a via the nozzle 430, and then exhausted from the exhaust pipe 231. At this time, the modified gas is supplied to the wafer 200. In addition, valve 534 is opened at the same time to circulate an inactive gas into the gas supply pipe 330. The inactive gas is flow-regulated by MFC532, and then supplied to the processing chamber 201 together with the modified gas, and then exhausted from the exhaust pipe 231. The second element film is modified by supplying the modified gas to the wafer 200.

[0094] After the modification of the second element film is completed, the valve 334 is closed to stop the supply of the modified gas. At this time, the APC valve 243 is kept open to exhaust the inside of the processing chamber 201, and the residual modified gas in the processing chamber 201 is removed from the processing chamber 201. In addition, the valve 534 is kept open to maintain the supply of the inactive gas to the processing chamber 201. The inactive gas acts as a purge gas.

[0095] In step (d), step Ge(b) and step R(c) are performed m times (m is an integer greater than 1 or 2).

[0096] In step (d), a second element film B is formed through step Ge(b) and step R(c). Here, in step Ge(b) and step R(c), a Ge seed layer is preferably formed as the second element film.

[0097] The processing conditions of step Ge(b) in step (d) include: second gas supply flow rate: 10-1000 sccm, second gas supply time: 0.1-30 minutes, inert gas supply flow rate: 10-3000 sccm, processing temperature: 250-650°C, and processing pressure: 1-1000 Pa.

[0098] Here, as the second gas, a gas containing Ge element as the second element is preferred. In addition, as the second gas, a gas having at least one organic group in one molecule is preferred. The organic group is a group bonded to the second element. Specifically, as the second gas, a gas having the structure of the formula: RGeX is preferred. Wherein, in the formula, R is a group (also called a residue, a substituent, a ligand), for example, an organic group can be cited. The gas having an organic group is preferably a gas containing at least any one of methyl (CH3-), vinyl (C2H3-), ethyl (C2H5-), isopropyl (C3H7-) and butyl (C4H9-) as the organic group R. Among them, the gas containing butyl (C4H9-) as the organic group also includes isomers. X in the formula includes: at least any one of: a hydrogen (H) atom, the above-mentioned organic group, and an amino group. Specific examples of the second gas include tert-butylgermane (tert-BuGeH3) gas, dimethylaminogermanium gas, diethylaminogermanium gas, bis(methylamino)germanium gas, bis(diethylamino)germanium gas, and tris(dimethylamino)germanium gas.

[0099] The processing conditions of step R(c) in step (d) include: modified gas supply flow rate: 10 to 1000 sccm, modified gas supply time: 0.1 to 30 minutes, inert gas supply flow rate: 10 to 3000 sccm, processing temperature: 250 to 650°C, and processing pressure: 1 to 1000 Pa.

[0100] Here, the modified gas is a gas that makes the density of adsorption sites on the inner surface of the pores of the membrane uniform. Examples of the modified gas include: a gas having a halogen group, a gas having an amino group, and a plasma-excited gas. Among these, from the viewpoint of homogenization of the membrane, a gas having an amino group and a plasma-excited gas are preferred. A gas having a halogen group is one that causes the halogen group to be adsorbed on the membrane. Examples of gases having a halogen group include: HCl, Cl2, NF3, etc. A gas having an amino group is one that causes the amino group to be adsorbed on the membrane. Examples of gases having an amino group include triethylamine, etc. A plasma-excited gas is one that causes H, NH, and O to be adsorbed on the membrane to remove unnecessary groups of the membrane. Examples of plasma-excited gases include: H2, D2, He, N2, O2, Ar, NH3, and ND3.

[0101] In step (d), the number of cycles of steps Ge(b) and R(c) can be 1 to 300. In addition, the thickness of the formed second element film B can be 1 to 20 nm, for example.

[0102] - Step (e) -

[0103] In step (e), step Si (a) and step R (c) are performed l times (l is an integer greater than 1 or 2) after step (d).

[0104] In step (e), step Si(a) is performed first. In step Si(a), a first gas containing a first element is supplied to the wafer 200 in the processing chamber 201. Specifically, valve 314 is opened to circulate the first gas into the gas supply pipe 310. The first gas is flow-adjusted by MFC312, and then supplied to the processing chamber 201 from the gas supply port 410a via the nozzle 410, and then exhausted from the exhaust pipe 231. At this time, the first gas is supplied to the wafer 200. In addition, valve 514 is opened at the same time to circulate an inactive gas into the gas supply pipe 310. The inactive gas is flow-adjusted by MFC512, and then supplied to the processing chamber 201 together with the first gas, and then exhausted from the exhaust pipe 231. By supplying the first gas containing the first element to the wafer 200, an amorphous, epitaxial or complex crystalline first element film is formed.

[0105] After the formation of the first element film C is completed, the valve 314 is closed to stop the supply of the first gas. At this time, the processing chamber 201 is exhausted while the APC valve 243 is kept open, and the first gas remaining in the processing chamber 201 is removed from the processing chamber 201. In addition, the supply of the inactive gas to the processing chamber 201 is maintained while the valve 514 is kept open. The inactive gas acts as a purge gas.

[0106] Next, step R(c) is performed in step (d). In step R(c), a modified gas is supplied to the wafer 200 in the processing chamber 201. Specifically, valve 334 is opened to circulate the modified gas into the gas supply pipe 330. The modified gas is flow-regulated by MFC332, and then supplied to the processing chamber 201 from the gas supply port 430a via the nozzle 430, and then exhausted from the exhaust pipe 231. At this time, the modified gas is supplied to the wafer 200. In addition, valve 534 is opened at the same time, and an inactive gas flows into the gas supply pipe 330. The inactive gas is flow-regulated by MFC532, and then supplied to the processing chamber 201 together with the modified gas, and then exhausted from the exhaust pipe 231. By supplying the modified gas to the wafer 200, the first element film is modified.

[0107] After the modification of the first element film is completed, the valve 334 is closed to stop the supply of the modified gas. At this time, the APC valve 243 is kept open to exhaust the process chamber 201, and the residual modified gas in the process chamber 201 is removed from the process chamber 201. In addition, the inert gas is kept supplied to the process chamber 201 while the valve 534 is kept open. The inert gas acts as a purge gas.

[0108] In step (e), step Si (a) and step R (c) are performed l times (l is an integer greater than 1 or 2).

[0109] Step (e) Forming a modified first element film C through step Si(a) and step R(c) Here, it is preferable to form a Si layer as the first element film A in step Si(a) and step R(c).

[0110] The processing conditions of step Si(a) in step (e) can be exemplified as: first gas supply flow rate: 10~1000sccm, first gas supply time: 0.1~30 minutes, inert gas supply flow rate: 10~3000sccm, processing temperature: 250~650℃, processing pressure: 1~1000Pa.

[0111] Here, the first gas preferably contains Si as the first element. Examples of the first gas include the same gases as those described in step (a1) of step (d).

[0112] The processing conditions of step R(c) in step (e) can be exemplified as: modified gas supply flow rate: 10~3000sccm, modified gas supply time: 0.1~30 minutes, inert gas supply flow rate: 10~3000sccm, processing temperature: 250~650℃, processing pressure: 1~1000Pa.

[0113] Examples of the reforming gas include the same gases as those described in step R(c) of step (d).

[0114] In step (d), the number of cycles of steps Si(a) and R(c) can be, for example, 1 to 300. The thickness of the formed first element film C can be, for example, 1 to 20 nm.

[0115] (Purge and atmospheric pressure restoration)

[0116] After the film formation is completed, an inert gas such as N2 gas is supplied from the gas supply pipes 510, 520, and 530 to the processing chamber 201, and the gas is exhausted from the exhaust pipe 231. The inert gas acts as a purge gas, and thus the processing chamber 201 is purged with the inert gas to remove the residual gas and by-products in the processing chamber 201 from the processing chamber 201. Then, the atmosphere in the processing chamber 201 is replaced with the inert gas, and the pressure in the processing chamber 201 is restored to normal pressure (atmospheric pressure).

[0117] (Substrate removal)

[0118] Then, the sealing cap 219 is lowered by the wafer box elevator 115 to open the lower end of the MF 209. Then, the processed wafer 200 is carried out from the lower end of the reaction tube 203 to the outside of the reaction tube 203 while being supported by the wafer box 217. Then, the processed wafer 200 is taken out from the wafer box 217.

[0119] [Results of this embodiment]

[0120] According to this embodiment, one or more of the following effects A) to H) can be obtained. Therefore, according to the present disclosure, it is possible to contribute to the miniaturization of semiconductor devices in the future.

[0121] A) A film containing a Group 14 element can be formed thinly, flatly, and uniformly.

[0122] B) It can improve the electrical performance of the channel film of the semiconductor device.

[0123] C) The film containing the Group 14 element can be utilized as a sacrificial etching film for the silicon film.

[0124] D) The first element film A is formed as a seed layer of the second element film B. By having the first element film A, the second element film B can be uniformly formed on the substrate.

[0125] E) In the process of forming the second element film B (i.e., step (d)), by supplying the second gas and the modifying gas, the second element can be uniformly adsorbed on the substrate while removing elements (groups) other than the second element contained in the second gas. That is, the formation of steric hindrance caused by the molecules of the second gas itself can be suppressed. As a result, the second element can be uniformly adsorbed on the substrate.

[0126] F) In step (d), by using a gas having an organic group as the second gas, for example, under conditions for forming a second element film B, the adsorption of the second element on the substrate can be promoted. As a result, the second element can be uniformly formed on the substrate. A seed layer containing the second element can be formed.

[0127] G) In the process of forming the film C containing the first element (i.e., step (e)), by supplying the first gas and the modifying gas, the first element can be uniformly adsorbed on the substrate while removing elements (groups) other than the first element contained in the first gas. That is, the formation of steric hindrance caused by the molecules of the first gas itself can be suppressed. As a result, the first element can be uniformly adsorbed on the substrate.

[0128] H) By using a gas containing an amine group as a modifying gas, it is possible to remove elements (groups) other than the Group 14 element from the gas containing the Group 14 element (i.e., the first gas and the second gas) while allowing the NH- group to be adsorbed on the substrate surface. By adsorbing the NH- group on the substrate surface, the adsorption of the gas containing the Group 14 element (i.e., the first gas and the second gas) supplied next can be improved. That is, the formation of steric hindrance caused by the gas molecules containing the Group 14 element itself can be suppressed. As a result, the Group 14 element can be uniformly adsorbed on the substrate.

[0129] I) By using a gas converted to plasma as a modified gas, it is possible to remove elements (groups) other than the Group 14 element from the gas containing the Group 14 element (i.e., the first gas and the second gas) while allowing the elements contained in the plasma to be adsorbed on the substrate surface. That is, the formation of steric hindrance caused by the molecules containing the first gas and the second gas itself can be suppressed. As a result, the Group 14 element can be uniformly adsorbed on the substrate while the elements contained in the plasma can be adsorbed on the substrate surface. The elements contained in the plasma refer to, for example, at least one or more of H, NH and O. By allowing at least one or more of these to be adsorbed, the adsorption of the gas containing the Group 14 element (i.e., the first gas and the second gas) supplied next can be improved.

[0130] J) By using a gas having a halogen group as a modified gas, it is possible to remove elements (groups) other than the 14th group element from the gas containing the 14th group element (i.e., the first gas and the second gas) while adsorbing the halogen on the substrate surface. Halogen is, for example, chlorine (Cl). Halogen has the property of easily reacting with H and CHx- in the gas containing the 14th group element (i.e., the first gas and the second gas). Halogen reacts with H and CHx- in the gas containing the 14th group element, and can remove groups such as H and CHx- from the gas containing the 14th group element. When the halogen is Cl, it is detached as HCl and CHxCl. As a result, the adsorption of the gas containing the 14th group element to the substrate surface can be promoted. In addition, by reacting and detaching the halogen on the substrate surface with H and CHx- in the gas containing the 14th group element, at least a portion of the gas containing the 14th group element can be adsorbed on the substrate surface.

[0131] [Modifications]

[0132] This embodiment is not limited to Figure 4 The method can also be changed into the following modified examples. These modified examples can be combined arbitrarily. Unless otherwise specified, the processing process and processing conditions of each step of each modified example can be set to be the same as the processing process and processing conditions of each step of the above-mentioned film forming sequence.

[0133] For example, in this embodiment, in step (d), in addition to steps Ge(b) and R(c), step Si(a) may also be performed. That is, in step (d), a film containing the first element and the second element may also be formed. In this embodiment, specifically, a film containing Si element as the first element and Ge element as the second element (more specifically, a SiGe seed layer) may also be formed. Here, the processing conditions of step Si(a) in step (d) may also be set to be the same as the processing conditions of step Si(a) in step (e).

[0134] In addition, in this embodiment, in step (e), in addition to step Si (a) and R (c), step Ge (b) may be performed. That is, in step (e), a film containing the first element and the second element may be formed. Thus, in this embodiment, specifically, a film containing Si as the first element and Ge as the second element (more specifically, a SiGe layer) may be formed.

[0135] In addition, in the present embodiment, in steps (d) and (e), except for the first step Si(a1), the steps performed after each step of steps Si(a), Ge(b) and R(c) can also be implemented in a manner that has a time of being performed simultaneously with the previously performed steps. Two or more steps having the same time means that the processing period of each step overlaps, and the start and end of each step can be the same time, or the start and end of each step can be different. When two or more processes have the same time, for convenience, each step is additionally marked as "+". Specifically, for example, when processes Si(a), Ge(b) and R(c) have the same time, it is sometimes marked as follows. The same expression is also used in the following descriptions of other methods, variations, etc.

[0136] (Si(a)+Ge(b)+R(c))

[0137] In steps (d) and (e), except for the first step Si(a1), if the processes performed after each of steps Si(a), Ge(b) and R(c) are performed at the same time as the previously performed processes, the film formation time can be shortened.

[0138] Hereinafter, specific modified examples of the present embodiment will be described.

[0139] (Variant 1) (d) [Si(a1)×n]→[(Ge(b)+R(c))×n]

[0140] like Figure 5 As shown, in step (d), there may be a moment when step Ge(b) and step R(c) are performed simultaneously.

[0141] (Variant 2) (d) [Si(a1)×n]→[(Ge(b)+Si(a1)→R(c))×n]

[0142] like Figure 6 As shown, in step (d), there may be a moment when steps Si(a), Ge(b) and R(c) are performed after step Si(a1), and step Ge(b) and step Si(a) are performed simultaneously.

[0143] (Variant 3) (d) [Si(a1)×n]→[(Ge(b)+Si(a1)+R(c))×n]

[0144] like Figure 7 As shown, in step (d), there may be a moment when steps Si(a), Ge(b) and R(c) are performed after step Si(a1), and step Ge(b), step Si(a) and step R(c) are performed simultaneously.

[0145] (Variant 4) (d) [Si(a1)×n]→[(Ge(b)→Si(a1)→R(c))×n]}

[0146] like Figure 8 As shown, in step (d), there may be a moment when step Si(a), step Ge(b) and R(c) are performed after step Si(a1), and step Si(a) is performed after step Ge(b). In addition, in this embodiment, step Si(a) is performed before step R(c).

[0147] (Variant 5) (d) [Si(a1)×n]→[(Ge(b)→Si(a1)+R(c))×n]}

[0148] like Fig. 9 As shown, steps Si(a), Ge(b) and R(c) are performed after step (a1), and steps Si(a) and R(c) are performed simultaneously after step Ge(b).

[0149] (Variant 6) (e) [(Si(a) + R(c)) × n]

[0150] like Fig.10 As shown, in step (e), there may be a moment when steps Ge(b) and R(c) are performed simultaneously.

[0151] (Variant 7) (e) [(Si(a) + Ge(b) + R(c)) × n]

[0152] like Fig.11 As shown, step Si(e) may include the time when steps Si(a), Ge(b) and R(c) are performed, and steps Si(a), Ge(b) and R(c) are performed simultaneously.

[0153] (Variant 8) (e) [(Si(a)+R(c)→Ge(b))×n]

[0154] like Fig.12 As shown, there may be a moment in which steps Si(a), Ge(b) and R(c) are performed, and steps Si(a) and R(c) are performed at the same time, after which step Ge(b) is performed.

[0155] In addition, in this example, there may be a moment in which steps Si(a), Ge(b) and R(c) are performed, and steps Si(a) and R(c) are performed at the same time, and step Ge(b) is performed before this moment.

[0156] (e)[(Ge(b)→Si(a)+R(c))×n]

[0157] [Other methods]

[0158] The embodiments of the present disclosure have been specifically described above, but the present disclosure is not limited to the above embodiments, and various modifications can be made without departing from the gist of the present disclosure.

[0159] The recipes for substrate processing are preferably prepared separately according to the processing content, and stored in the storage device 121c via the communication circuit and the external storage device 123. Moreover, it is preferred that when starting the processing, the CPU 121a appropriately selects a suitable recipe from the multiple recipes stored in the storage device 121c according to the content of the substrate processing. Thus, a variety of film types, composition ratios, film qualities, and film thicknesses can be formed with good reproducibility by one substrate processing device. In addition, the burden on the operator can be reduced, operational errors can be avoided, and various processes can be started quickly.

[0160] The above-mentioned recipe is not limited to the case of newly making, and can also be prepared by, for example, changing an existing recipe already installed in a substrate processing device. When changing a recipe, the changed recipe can be installed in the substrate processing device via a communication circuit or a recording medium recording the recipe. In addition, the input / output device 122 of the existing substrate processing device can be operated to directly change the existing recipe already installed in the substrate processing device.

[0161] In each of the above-mentioned steps of substrate processing, n times, m times, and l times may be the same number of times or different numbers of times.

[0162] In the above-mentioned method, an example of using a substrate processing device that processes multiple substrates at a time is described. The present disclosure is not limited to the above-mentioned method, and can also be well applied when, for example, a single-chip substrate processing device that processes one or more substrates at a time is used. In addition, in the above-mentioned method, an example of using a substrate processing device with a hot wall type processing furnace is described. The present disclosure is not limited to the above-mentioned method, and can also be well applied when a substrate processing device with a cold wall type processing furnace is used.

[0163] In addition, the above method describes an example in which the above processing sequence is performed in the same processing chamber of the same processing device (in-situ). The present disclosure is not limited to the above method, for example, any step in the above processing sequence and other steps can also be performed in different processing chambers of different processing devices (ex-situ), or can be performed in different processing chambers of the same processing device.

[0164] Even when these substrate processing apparatuses are used, film formation can be performed according to the same processing procedures and processing conditions as those in the above-mentioned embodiment and modified examples, and the same effects as these can be obtained.

[0165] In addition, the above-mentioned aspects, modifications, etc. may be used in combination as appropriate. The processing procedure and processing conditions in this case may be, for example, the same as the processing procedure and processing conditions in the above-mentioned aspects.

[0166] Explanation of symbols

[0167] 200 Wafer

Claims

1. A substrate processing method, characterized in that: include: (a) supplying a first gas containing a first Group 14 element to a substrate; (b) supplying a second gas containing a second Group 14 element to the substrate; (c) supplying a modified gas to the substrate; (d) a step of performing (a) n times, wherein n is an integer of 1 or 2 or more, to form a film containing the first Group 14 element, and then performing (b) and (c) at least m times, wherein m is an integer of 1 or 2 or more, to form a film containing at least the second Group 14 element; and (e) After step (d), the step of performing steps (a) and (c) at least once, wherein once is an integer of 1 or more, to form a film containing at least the first Group 14 element.

2. The substrate processing method according to claim 1, wherein: In (d), (c) is performed after (b).

3. The substrate processing method according to claim 1, wherein: (d) There is a moment when (b) and (c) are performed simultaneously.

4. The substrate processing method according to claim 1, wherein: In (d), (a), (b) and (c) are performed after (a), and (d) There is a moment when (b) and (a) are performed simultaneously.

5. The substrate processing method according to claim 2, wherein: In (d), (a), (b) and (c) are performed after (a), and (d) There is a moment when (b) and (a) are performed simultaneously.

6. The substrate processing method according to claim 4, wherein: In (d), (a), (b) and (c) are performed after (a), and (d) There is a moment when (b) and (a) are performed simultaneously.

7. The substrate processing method according to claim 2, wherein: In (d), (a), (b) and (c) are performed after (a), and (a) is performed after (b).

8. The substrate processing method according to claim 1, wherein: In (d), (a), (b) and (c) are performed after (a), and (d) There is a moment when (a) and (c) are performed simultaneously after (b).

9. The substrate processing method according to claim 1, wherein: (e) There is a moment when (a) and (c) are performed simultaneously.

10. The substrate processing method according to claim 1, wherein: In (e), (a), (b) and (c) are performed, and (e) There is a moment when (a), (b) and (c) are performed simultaneously.

11. The substrate processing method according to claim 1, wherein: In (e), (a), (b) and (c) are performed, and (e) There is a moment when (a) and (c) are performed simultaneously, and (b) is performed after that moment.

12. The substrate processing method according to claim 1, wherein: In (e), (c) is performed after (a).

13. The substrate processing method according to any one of claims 1 to 12, wherein: The first gas contains Si element as the first Group 14 element.

14. The substrate processing method according to any one of claims 1 to 12, wherein: The second gas contains Ge element as the second Group 14 element.

15. The substrate processing method according to any one of claims 1 to 12, wherein: The second gas has at least one organic group in one molecule.

16. The substrate processing method according to claim 15, wherein: The second gas is a gas containing at least any one of a methyl group, a vinyl group, an ethyl group, an isopropyl group, and a butyl group as the organic group.

17. The substrate processing method according to any one of claims 1 to 12, wherein: The modified gas includes a gas containing an amino group.

18. The substrate processing method according to any one of claims 1 to 12, wherein: The modified gas contains a plasma-excited gas.

19. A method for manufacturing a semiconductor device, characterized in that: include: (a) supplying a first gas containing a first Group 14 element to a substrate; (b) supplying a second gas containing a second Group 14 element to the substrate; (c) supplying a modified gas to the substrate; (d) a step of performing (a) n times, wherein n is an integer of 1 or 2 or more, to form a film containing the first Group 14 element, and then performing (b) and (c) at least m times, wherein m is an integer of 1 or 2 or more, to form a film containing at least the second Group 14 element; and (e) After (d), a step of performing (a) and (c) at least one time, wherein l is an integer of 1 or more, to form a film containing at least the first Group 14 element.

20. A program that causes a substrate processing device to execute the following process through a computer: (a) supplying a first gas containing a first Group 14 element to a substrate; (b) supplying a second gas containing a second Group 14 element to the substrate; (c) supplying a modifying gas to the substrate; (d) by performing (a) n times, where n is an integer of 1 or 2 or more, and after forming a film containing the first Group 14 element, a process of forming a film containing at least the second Group 14 element by performing (b) and (c) at least m times, wherein m is an integer of 1 or 2 or more; and (e) After step (d), a process of performing steps (a) and (c) at least once, wherein once is an integer of 1 or more, to form a film containing at least the first Group 14 element.

21. A substrate processing device, characterized in that: include: a first gas supply system for supplying a first gas containing a first Group 14 element to the substrate; a second gas supply system for supplying a second gas containing a second Group 14 element to the substrate; a modifying gas supply system for supplying a modifying gas to the substrate; and The control unit is configured to control the first gas supply system, the second gas supply system, and the modified gas supply system to perform the following processes: (a) a process of supplying a first gas containing a first Group 14 element to the substrate; (b) a process of supplying a second gas containing a second Group 14 element to the substrate; (c) a process of supplying a modified gas to the substrate; (d) after forming a film containing the first Group 14 element by performing (a) n times, where n is an integer greater than or equal to 1 or 2, a process of forming a film containing at least the second Group 14 element by performing (b) and (c) at least m times, where m is an integer greater than or equal to 1 or 2; and (e) after (d), a process of forming a film containing at least the first Group 14 element by performing (a) and (c) at least l times, where l is an integer greater than or equal to 1 or 2.

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