Substrate processing method, semiconductor device manufacturing method, substrate processing apparatus, and recording medium

Abstract

The present application has: (a) a process of supplying a first gas containing a semiconductor element and chlorine to a substrate to form a chlorine-containing semiconductor layer on an insulating film provided on a surface of the substrate; and (b) a process of supplying a second gas containing a semiconductor element to the substrate to form a semiconductor film on the chlorine-containing semiconductor layer, the chlorine concentration of the chlorine-containing semiconductor layer formed in (a) being set to 1.0 x 10 20 atoms / cm 3 or less. 22 atoms / cm 3 or more.

Description

Technical Field

[0001] This disclosure relates to substrate processing methods, semiconductor device manufacturing methods, substrate processing apparatus, and recording media. Background Technology

[0002] As a step in the manufacturing process of semiconductor devices, sometimes a step is performed to form a semiconductor film on an insulating film disposed on the surface of a substrate (see, for example, Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2014-175320 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] The purpose of this disclosure is to improve the characteristics of semiconductor devices.

[0008] Methods for solving problems

[0009] According to one aspect of this disclosure, a technology is provided that has:

[0010] (a) A step of supplying a first gas containing a semiconductor element and chlorine to a substrate, and forming a chlorine-containing semiconductor layer on an insulating film disposed on the surface of the substrate; and

[0011] (b) The step of supplying a second gas containing a semiconductor element to the aforementioned substrate and forming a semiconductor film on the aforementioned chlorine-containing semiconductor layer.

[0012] The chlorine concentration of the aforementioned chlorine-containing semiconductor layer formed in (a) is set to 1.0 × 10⁻⁶. 20 atoms / cm 3 Above 1.0×10 22 atoms / cm 3 the following.

[0013] Invention Effects

[0014] According to this disclosure, the characteristics of semiconductor devices can be improved. Attached Figure Description

[0015] [ Figure 1 ] Figure 1 This is a schematic diagram of a vertical processing furnace suitable for use in one embodiment of the present disclosure, and is a diagram showing the furnace portion in a longitudinal sectional view.

[0016] [ Figure 2 ] Figure 2This is a schematic diagram of a vertical processing furnace suitable for use in one embodiment of the present disclosure, and is based on... Figure 1 The diagram shows the processing furnace section using an AA-line sectional view.

[0017] [ Figure 3 ] Figure 3 This is a schematic configuration diagram of a controller for a substrate processing apparatus suitable for use in one embodiment of this disclosure, and is a block diagram illustrating the control system of controller 121.

[0018] [ Figure 4 ] Figure 4 A diagram illustrating the substrate processing sequence in one embodiment of this disclosure.

[0019] [ Figure 5 ] Figure 5 A plot diagram illustrating the relationship between chlorine concentration and dangling bond density in one embodiment of this disclosure. Detailed Implementation

[0020] <One way of publishing this text>

[0021] The following is for reference. Figures 1-4 This disclosure will be described in one manner. It should be noted that the accompanying drawings used in the following description are schematic diagrams, and the dimensional relationships and ratios of the elements in the drawings are not necessarily consistent with reality. Furthermore, the dimensional relationships and ratios of elements in multiple drawings are not necessarily consistent with each other.

[0022] (1) Composition of substrate processing device

[0023] like Figure 1 As shown, the processing furnace 202 has a heater 207 as a heating mechanism (temperature control unit). The heater 207 is cylindrical and is vertically mounted by being supported on a retaining plate. The heater 207 also functions as an activation mechanism (activation unit) that uses heat to activate (excite) the gas.

[0024] Inside the heater 207, a reaction tube 203 is arranged concentrically with the heater 207. The reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC) and is formed into a cylindrical shape with a closed upper end and an open lower end. Below the reaction tube 203, a manifold 209 is arranged concentrically with the reaction tube 203. The manifold 209 is made of a metal material such as stainless steel (SUS) and is formed into a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 to support the reaction tube 203. An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing component. The reaction tube 203 is also vertically mounted like the heater 207. The processing container (reaction container) is mainly composed of the reaction tube 203 and the manifold 209. A processing chamber 201 is formed in the hollow part of the processing container. The processing chamber 201 is configured to accommodate a wafer 200, which serves as a substrate. The wafer 200 is processed within this processing chamber 201.

[0025] Inside the processing chamber 201, nozzles 249a to 249c, serving as a first supply section to a third supply section, are respectively provided through the side wall of the manifold 209. These nozzles are also referred to as the first nozzle and the third nozzle, respectively. The nozzles 249a to 249c are constructed of a non-metallic material, such as quartz or SiC, which is heat-resistant. Gas supply pipes 232a to 232c are connected to each of the nozzles 249a to 249c. Each of the nozzles 249a to 249c is a different nozzle, and each of the nozzles 249a and 249c is positioned adjacent to the nozzle 249b.

[0026] On gas supply pipes 232a to 232c, mass flow controllers (MFCs) 241a to 241c, serving as flow controllers (flow control units), and valves 243a to 243c, serving as on / off valves, are sequentially installed from the upstream side of the airflow. Gas supply pipes 232d and 232f are connected to gas supply pipe 232a downstream of valve 243a. Gas supply pipes 232e and 232g are connected to gas supply pipe 232b downstream of valve 243b. On gas supply pipes 232d to 232g, MFCs 241d to 241g and valves 243d to 243g are sequentially installed from the upstream side of the airflow. Gas supply pipes 232a to 232g are made of a metal material such as SUS.

[0027] like Figure 2As shown, in the annular space between the inner wall of the reaction tube 203 and the wafer 200 (viewed from above), nozzles 249a to 249c are respectively provided vertically from the lower part of the inner wall of the reaction tube 203 upwards towards the arrangement direction of the wafer 200. That is, nozzles 249a to 249c are respectively provided along the wafer arrangement area, on the side of the wafer arrangement area where the wafer 200 is arranged, in a region that horizontally surrounds the wafer arrangement area. In view from above, nozzle 249b is arranged so as to clamp the center of the wafer 200 that has been moved into the processing chamber 201 and is aligned with the exhaust port 231a (described later) in a straight line. Nozzles 249a and 249c are arranged so as to clamp the straight line L passing through the center of nozzle 249b and exhaust port 231a from both sides along the inner wall of the reaction tube 203 (outer periphery of the wafer 200). Straight line L is also a straight line passing through the center of nozzle 249b and wafer 200. That is, nozzle 249c can also be positioned on the opposite side of nozzle 249a while clamping the straight line L. Nozzles 249a and 249c are arranged linearly symmetrically about the straight line L. Gas supply holes 250a and 250c for supplying gas are provided on the sides of nozzles 249a and 249c, respectively. Gas supply holes 250a and 250c open in a manner that is opposite to exhaust port 231a when viewed from above, and can supply gas to wafer 200. Multiple gas supply holes 250a and 250c are provided in the reaction tube 203 from bottom to top.

[0028] A gas (i.e., a chlorosilane-based gas) containing silicon (Si) and chlorine (Cl), which are semiconductor elements constituting the film formed on the wafer 200, is supplied as a first gas from the gas supply pipe 232a via MFC 241a, valve 243a, and nozzle 249a into the processing chamber 201. The chlorosilane-based gas contains chemical bonds between Si and Cl (Si-Cl bonds).

[0029] A gas containing, for example, Si (i.e., silane-based gas), which is a semiconductor element, is supplied as a second gas into the processing chamber 201 via the gas supply pipe 232b through MFC241b, valve 243b, and nozzle 249b.

[0030] A gas containing, for example, Si and hydrogen (H) as semiconductor elements (i.e., silicon hydride gas) is supplied as a third gas into the processing chamber 201 via gas supply pipe 232d, MFC 241d, valve 243d, gas supply pipe 232a, and nozzle 249a.

[0031] Gas, for example, H-containing gas, is supplied as a fourth gas into the processing chamber 201 via gas supply pipe 232e, MFC 241e, valve 243e, gas supply pipe 232b, and nozzle 249b.

[0032] Inactive gas is supplied to the treatment chamber 201 from gas supply pipes 232c, 232f, and 232g via MFCs 241c, 241f, and 241g, valves 243c, 243f, and 243g, gas supply pipes 232a to 232c, and nozzles 249a to 249c, respectively. The inactive gas functions as a purge gas, carrier gas, and dilution gas.

[0033] The first gas supply system mainly consists of gas supply pipe 232a, MFC 241a, and valve 243a. The second gas supply system mainly consists of gas supply pipe 232b, MFC 241b, and valve 243b. The third gas supply system mainly consists of gas supply pipe 232d, MFC 241d, and valve 243d. The fourth gas supply system mainly consists of gas supply pipe 232e, MFC 241e, and valve 243e. The inactive gas supply system mainly consists of gas supply pipes 232c, 232f, 232g, MFCs 241c, 241f, 241g, and valves 243c, 243f, 243g.

[0034] Any or all of the aforementioned gas supply systems can be configured as an integrated gas supply system 248, which integrates valves 243a-243g, MFCs 241a-241g, etc. The integrated gas supply system 248 is connected to the gas supply pipes 232a-232g, and is configured such that the controller 121 (described later) controls the supply of various gases into the gas supply pipes 232a-232g, i.e., the opening and closing of valves 243a-243g, and the flow regulation using MFCs 241a-241g. The integrated gas supply system 248 is configured as an integrated unit, either as a single unit or as separate units, allowing for the assembly and disassembly of the gas supply pipes 232a-232g, and enabling maintenance, replacement, and addition of the integrated gas supply system 248 on a unit-by-unit basis.

[0035] Below the side wall of the reaction tube 203, there is an exhaust port 231a for exhausting the atmosphere inside the processing chamber 201. Figure 2As shown, the exhaust port 231a is positioned opposite the nozzles 249a-249c (gas supply holes 250a-250c) when the wafer 200 is clamped in a top view. The exhaust port 231a can also be positioned from the lower part of the side wall of the reaction tube 203 along the upper part, i.e., along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a. A vacuum pump 246, serving as a vacuum exhaust device, is connected to the exhaust pipe 231 via a pressure sensor 245 (a pressure detector, or pressure detection unit) that detects the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 (a pressure regulator, or pressure regulating unit). The APC valve 244 is configured to open and close while the vacuum pump 246 is operating, thereby enabling vacuum exhaust and stopping of vacuum exhaust within the processing chamber 201. Furthermore, by adjusting the valve opening based on the pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating, the pressure within the processing chamber 201 can be adjusted. The exhaust system mainly consists of an exhaust pipe 231, an APC valve 244, and a pressure sensor 245. Alternatively, a vacuum pump 246 could be included in the exhaust system.

[0036] Below the manifold 209, a sealing cover 219, serving as a furnace opening cover, is provided to airtightly seal the lower opening of the manifold 209. The sealing cover 219 is made of a metal material such as SUS and is formed in a disc shape. On the upper surface of the sealing cover 219, an O-ring 220b, serving as a sealing member, abuts against the lower end of the manifold 209. Below the sealing cover 219, a rotation mechanism 267 is provided to rotate the crystal boat 217 (described later). The rotation shaft 255 of the rotation mechanism 267 passes through the sealing cover 219 and is connected to the crystal boat 217. The rotation mechanism 267 is configured to rotate the wafer 200 by rotating the crystal boat 217. The sealing cover 219 is configured to be vertically raised and lowered by a crystal boat lift 115, which is a lifting mechanism located outside the reaction tube 203. The crystal boat lift 115 is configured as a transport device (transport mechanism) that moves the wafer 200 into and out of the processing chamber 201 by raising and lowering the sealing cover 219.

[0037] Below the manifold 209, a gate 219s serving as a furnace opening cover is provided. This gate 219s can airtightly seal the lower opening of the manifold 209 after the sealing cover 219 has been lowered and the crystal boat 217 has been removed from the processing chamber 201. The gate 219s is made of a metal material such as SUS and is formed in a disc shape. On the upper surface of the gate 219s, an O-ring 220c serving as a sealing component abuts against the lower end of the manifold 209. The opening and closing actions (lifting, rotating, etc.) of the gate 219s are controlled by a gate opening and closing mechanism 115s.

[0038] The crystal boat 217, serving as a substrate support, is configured to support multiple wafers 200 (e.g., 25 to 200 wafers) arranged vertically in a horizontal orientation with their centers aligned, in a multi-layered manner, i.e., spaced apart. The crystal boat 217 is made of a heat-resistant material such as quartz or SiC. The lower part of the crystal boat 217 supports a heat-insulating plate 218 made of a heat-resistant material such as quartz or SiC in multiple layers.

[0039] A temperature sensor 263, serving as a temperature detector, is installed inside the reaction tube 203. By adjusting the energizing state of the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature within the processing chamber 201 is adjusted to achieve the desired temperature distribution. The temperature sensor 263 is disposed along the inner wall of the reaction tube 203.

[0040] like Figure 3 As shown, the controller 121, serving as the control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, RAM (Random Access Memory) 121b, a storage device 121c, and an I / O port 121d. The RAM 121b, storage device 121c, and I / O port 121d are configured to exchange data with the CPU 121a via an internal bus 121e. An input / output device 122, such as a touch panel, is connected to the controller 121. Furthermore, an external storage device 123 can be connected to the controller 121.

[0041] Storage device 121c is composed of, for example, flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), etc. Storage device 121c stores in a readable manner a control program that controls the operation of the substrate processing apparatus, and a process flow that describes the substrate processing steps and conditions, as described later. The process flow is a combination of methods that enable controller 121 to execute each step of the substrate processing described later and obtain a specified result, and functions as a program. Hereinafter, process flow, control program, etc., will also be referred to as a program. Furthermore, process flow will be referred to simply as a process. In this specification, the term "program" is used in cases where only a process flow is included, cases where only a control program is included, or cases where both are included. RAM 121b is configured as a storage area (working area) for temporarily holding programs, data, etc., read by CPU 121a.

[0042] I / O port 121d is connected to the aforementioned MFC241a~241g, valves 243a~243g, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotating mechanism 267, crystal boat elevator 115, gate opening and closing mechanism 115s, etc.

[0043] CPU 121a is configured to read and execute control programs from storage device 121c, and to read processes from storage device 121c based on input of operation commands from input / output device 122. CPU 121a is configured to control the following actions according to the read processes: flow regulation of various gases using MFCs 241a to 241g, opening and closing of valves 243a to 243g, opening and closing of APC valve 244 and pressure regulation using APC valve 244 based on pressure sensor 245, starting and stopping of vacuum pump 246, temperature regulation of heater 207 based on temperature sensor 263, rotation and rotation speed regulation of crystal boat 217 using rotating mechanism 267, lifting and lowering of crystal boat 217 using crystal boat elevator 115, opening and closing of gate 219s using gate opening and closing mechanism 115s, etc.

[0044] The controller 121 is configured to install the aforementioned program stored in the external storage device 123 into a computer. The external storage device 123 includes, for example, hard disks such as HDDs, optical disks such as CDs, optical disks such as MO drives, USB storage devices, and semiconductor storage devices such as SSDs. The storage device 121c and the external storage device 123 are configured in the form of a computer-readable recording medium. Hereinafter, they will also be referred to collectively as recording media. In this specification, the term "recording medium" is used in cases where only the storage device 121c is included, cases where only the external storage device 123 is included, or cases where both are included. It should be noted that providing a program to a computer may also be done without using the external storage device 123, but using communication means such as the Internet or dedicated lines.

[0045] (2) Substrate processing process

[0046] An example of a substrate processing sequence in which the aforementioned substrate processing apparatus is used to form a semiconductor film on an insulating film disposed on the surface of a wafer 200 serving as a substrate, as a step in the manufacturing process of a semiconductor device, primarily using... Figure 4 The following description will explain the operation of each part constituting the substrate processing apparatus, which is controlled by controller 121.

[0047] like Figure 4 As shown, the substrate processing sequence in this method includes the following steps:

[0048] Step A (forming a Cl-containing Si layer) involves supplying a chlorosilane-based gas as a first gas to the wafer 200 and forming a Cl-containing Si layer as a chlorine-containing semiconductor layer on a silicon oxide film (SiO film) that serves as an insulating film disposed on the surface of the wafer 200; and

[0049] Step B (forming a Si film): A silane-based gas is supplied to the wafer 200 as a second gas to form a silicon film (Si film) as a semiconductor film on a Cl-containing Si layer.

[0050] The Cl concentration of the Cl-containing Si layer formed in step A is set to 1.0 × 10⁻⁶. 20 atoms / cm 3 Above 1.0×10 22 atoms / cm 3 the following.

[0051] It should be noted that in step A, the following processes will be performed cyclically a specified number of times (n times, where n is an integer greater than or equal to 1): step A1, which supplies chlorosilane-based gas to wafer 200, and step A2, which uses inactive gas to purge the space in which wafer 200 exists to remove residual chlorosilane-based gas in the space.

[0052] In addition, in the substrate processing sequence of this method, after performing step B, step C (annealing) is further performed to anneal the Si layer and Si film containing Cl.

[0053] For convenience, the substrate processing sequence described above is sometimes shown in this specification as follows. The same wording is used in the following descriptions of variations, etc. It should be noted that "ANL" in the following descriptions indicates annealing.

[0054] (chlorosilane-based gases → inactive gases) × n → silane-based gases → ANL

[0055] In this specification, the term "wafer" is used to refer to both the wafer itself and a laminate of the wafer and a specified layer or film formed on its surface. The term "surface of the wafer" is used to refer to the surface of the wafer itself and the surface of a specified layer, etc., formed on the wafer. The phrase "forming a specified layer on the wafer" includes forming the specified layer directly on the surface of the wafer itself and forming the specified layer on top of a layer, etc., formed on the wafer. The term "substrate" is used in the same way as "wafer."

[0056] (Wafer filling and crystal boat loading)

[0057] If multiple wafers 200 are loaded (wafer filling) into the crystal boat 217, the gate opening and closing mechanism 115s moves the gate 219s, opening the lower end of the manifold 209 (gate opening). Then, as... Figure 1 As shown, a crystal boat 217 supporting multiple wafers 200 is lifted by a crystal boat lift 115 and moved into the processing chamber 201 (crystal boat loading). In this state, the sealing cap 219 seals the lower end of the manifold 209 by means of an O-ring 220b.

[0058] A SiO film is pre-formed on the surface of wafer 200 as an insulating film. The insulating film can be a silicon oxynitride film (SiON film). Preferably, the insulating film is a substantially Cl-free film, i.e., a Cl-free film.

[0059] (Pressure and temperature regulation)

[0060] Vacuum pump 246 performs vacuum venting (pressure reduction venting) to achieve the desired pressure (vacuum level) within processing chamber 201, i.e., the space where wafer 200 exists. At this time, the pressure within processing chamber 201 is measured by pressure sensor 245, and APC valve 244 is controlled based on this measured pressure information. Additionally, wafer 200 within processing chamber 201 is heated using heater 207 to achieve the desired processing temperature. At this time, the energization state of heater 207 is controlled based on temperature information detected by temperature sensor 263 to achieve the desired temperature distribution within processing chamber 201. Furthermore, rotation of wafer 200 is initiated using rotation mechanism 267. Venting within processing chamber 201, heating of wafer 200, and rotation are all performed continuously, at least until the processing of wafer 200 is completed.

[0061] (Step A: Forming a Cl-containing Si layer)

[0062] Then, perform the following steps A1 and A2 in sequence.

[0063] [Step A1]

[0064] In this step, chlorosilane-based gas is supplied to the wafer 200 in the processing chamber 201, that is, to the SiO film disposed on the surface of the wafer 200.

[0065] Specifically, valve 243a is opened, allowing chlorosilane-based gas to flow into gas supply pipe 232a. The flow rate of the chlorosilane-based gas is regulated by MFC 241a, supplied to processing chamber 201 via nozzle 249a, and exhausted from exhaust port 231a. At this time, chlorosilane-based gas is supplied to wafer 200. At this time, valves 243c, 243f, and 243g can be opened, supplying inactive gas into processing chamber 201 via nozzles 249a to 249c respectively.

[0066] By supplying a chlorosilane-based gas to the wafer 200 under the processing conditions described later, Si contained in the chlorosilane-based gas can be adsorbed (deposited) onto the SiO film disposed on the surface of the wafer 200 while Cl is bonded to Si. That is, Si contained in the chlorosilane-based gas can be adsorbed onto the SiO film without breaking the chemical bond (Si-Cl bond) between Si and Cl.

[0067] [Step A2]

[0068] After the specified time has elapsed, valve 243a is closed, stopping the supply of chlorosilane-based gas to the processing chamber 201. Simultaneously, a vacuum is purged from the processing chamber 201 to remove any remaining gases (purge). At this point, valves 243c, 243f, and 243g are opened, supplying an inert gas to the processing chamber 201. This inert gas serves as the purging gas.

[0069] [Number of times stipulated for implementation]

[0070] By alternately, i.e. asynchronously and non-simultaneously, performing the above steps A1 and A2 cyclically a predetermined number of times (n times, where n is an integer greater than or equal to 1), a silicon layer (Si layer) containing a high concentration of Cl, i.e., a Cl-containing Si layer, can be formed on the SiO film disposed on the surface of the wafer 200. The Cl-containing Si layer becomes the layer constituting the interface between the SiO film as an insulating film and the Si film as a semiconductor film described later. The Cl-containing Si layer becomes a Cl-containing amorphous (non-crystalline) Si layer.

[0071] The Cl concentration in the Cl-containing Si layer is set to, for example, 1.0 × 10⁻⁶. 20 atoms / cm 3 Above 1.0×10 22 atoms / cm 3 The following is preferably set to 3.0 × 10 20 atoms / cm 3 Above 5.0×10 21 atoms / cm 3 the following.

[0072] Preferably, the thickness of the Cl-containing Si layer is thinner than that of the SiO film and the Si film (described later) disposed on the surface of the wafer 200. The thickness of the Cl-containing Si layer is, for example, set to one monolayer (or less, ML) or more. (3nm) or below, preferably set as (0.25nm) and above (3nm) or less, preferably set to (0.3nm) and above (Below 2nm). It should be noted that 1ML refers to a monolayer or a single atomic layer.

[0073] The Cl concentration and thickness of the Cl-containing Si layer can be controlled by one or more of the following in step A1: processing temperature (temperature of wafer 200), processing pressure (pressure of the space in which wafer 200 exists), supply flow rate of chlorosilane gas, and supply time of chlorosilane gas. Therefore, the dangling bond density at the interface between the SiO film (which serves as an insulating film) and the Si film (which will be described later as a semiconductor film) can be controlled.

[0074] Furthermore, the Cl concentration and thickness of the Cl-containing Si layer can be controlled by the number of cycles (n times) described in step A. This allows for control of the dangling bond density at the interface between the SiO film (which serves as an insulating film) and the Si film (which serves as a semiconductor film, described later).

[0075] As a processing condition in step A1, the following examples can be given:

[0076] Chlorosilane gas supply flow rate: 0.1~1slm

[0077] Chlorosilane gas supply time: 0.5–2 minutes

[0078] Processing temperature (first temperature): 350–450℃, preferably 350–400℃

[0079] Processing pressure: 277~1200Pa (2~9Torr), preferably 667~1200Pa (5~9Torr).

[0080] As a processing condition in step A2, the following examples can be given:

[0081] Inactive gas supply flow rate: 0.5–20 slm

[0082] Inactive gas supply time: 10–30 seconds

[0083] Processing pressure: 1-30 Pa.

[0084] Other processing conditions can be the same as those in step A1.

[0085] It should be noted that the numerical range "350~450℃" in this specification refers to the inclusion of both the lower and upper limits within that range. Therefore, for example, "350~450℃" means "above 350℃ and below 450℃". The same applies to other numerical ranges.

[0086] As the first gas (a chlorosilane-based gas), for example, monochlorosilane (SiH3Cl, abbreviated as MCS), dichlorosilane (SiH2Cl2, abbreviated as DCS), trichlorosilane (SiHCl3, abbreviated as TCS), tetrachlorosilane (SiCl4, abbreviated as STC), hexachlorodisilane (Si2Cl6, abbreviated as HCDS), octachlorotrisilane (Si3Cl8, abbreviated as OCTS), and other chlorosilane-based gases can be used. This is also true in the subsequent steps and variations.

[0087] In addition to nitrogen (N2), other rare gases such as argon (Ar), helium (He), neon (Ne), and xenon (Xe) can also be used as inert gases. This is also true in the subsequent steps and variations.

[0088] (Temperature rising)

[0089] After step A is completed, i.e., after the formation of the Cl-containing Si layer on the SiO film is finished, the output power of heater 207 is adjusted to change the temperature inside processing chamber 201, i.e., the temperature of wafer 200, to a second temperature higher than the first temperature described above. During this step, valves 243c, 243f, and 243g are opened, and inactive gas is supplied into processing chamber 201 through nozzles 249a to 249c, and exhaust is performed from exhaust port 231a, thus purging processing chamber 201. After the temperature of wafer 200 reaches and stabilizes at the second temperature, step B, described later, begins.

[0090] (Step B: Si film formation)

[0091] After the temperature of wafer 200 reaches the second temperature, silane-based gas is supplied to wafer 200, i.e., the Si layer containing Cl formed on wafer 200, in processing chamber 201.

[0092] Specifically, valve 243b is opened, allowing silane-based gas to flow into gas supply pipe 232b. The flow rate of the silane-based gas is regulated by MFC 241b, supplied to processing chamber 201 via nozzle 249b, and exhausted from exhaust port 231a. At this time, silane-based gas is supplied to wafer 200. At this point, valves 243c, 243f, and 243g can be opened, supplying inactive gas into processing chamber 201 via nozzles 249a to 249c respectively.

[0093] By supplying a silane-based gas to the wafer 200 under the processing conditions described later, the silane-based gas can be decomposed in the gas phase, causing Si to be adsorbed (accumulated) on the surface of the wafer 200, i.e., on the Cl-containing Si layer formed on the SiO film, thus forming a Si film. By using a Cl-free silane-based gas as a second gas, the Si film formed on the wafer 200 can be made into a Cl-free film.

[0094] It should be noted that in step B, the Si film formed on the Cl-containing Si layer becomes an amorphous (non-crystalline) Si film, or a mixed-crystal Si film of amorphous and polycrystalline states. Furthermore, at this time, a portion of the Cl-containing Si layer becomes polycrystalline, and the Cl-containing Si layer also becomes a mixed-crystal Si layer containing Cl, comprising both amorphous and polycrystalline states.

[0095] After a specified time, valve 243b is closed to stop the supply of silane gas to the processing chamber 201. Then, using the same processing steps and conditions as in step A2, the residual gas in the processing chamber 201 is discharged from the processing chamber 201.

[0096] As a processing condition in step B, an example can be shown:

[0097] Silane-based gas supply flow rate: 0.01~5slm

[0098] Silane-based gas supply time: 1–300 minutes

[0099] Inactive gas supply flow rate (per gas supply pipe): 0–20 slm

[0100] Processing temperature (second temperature): 450~550℃

[0101] Processing pressure: 30-400 Pa (1.5-3 Torr).

[0102] As the second gas (silane-based gas), for example, monosilane (SiH4), disilane (Si2H6), trisilane (Si3H8), and tetrasilane (Si4H6) can be used. 10 ) gas, pentasilane (Si5H) 12 ) gas, hexasilane (Si6H) 14The gases used are hydride gases, tetra(dimethylamino)silane (Si[N(CH3)2]4, abbreviated as 4DMAS), tri(dimethylamino)silane (Si[N(CH3)2]3H, abbreviated as 3DMAS), bis(diethylamino)silane (Si[N(C2H5)2]2H2, abbreviated as BDEAS), and bis(tert-butylamino)silane (SiH2[NH(C4H9)]2, abbreviated as BTBAS), and other aminosilane-based gases. It should be noted that, if considering the suppression of impurities such as H, N, and C from entering the Si film formed in step B, hydride gases that do not contain N and C are preferred as the silane-based gases.

[0103] (Temperature rising)

[0104] After step B is completed, i.e., after the formation of the Si film on the Cl-containing Si layer is finished, the output power of heater 207 is adjusted to change the temperature inside processing chamber 201, i.e., the temperature of wafer 200, to a third temperature higher than the second temperature mentioned above. During this step, valves 243c, 243f, and 243g are opened, and inactive gas is supplied into processing chamber 201 through nozzles 249a to 249c, and exhaust is performed from exhaust port 231a, thus purging processing chamber 201. After the temperature of wafer 200 reaches and stabilizes at the third temperature, step C, described later, begins.

[0105] (Step C: Annealing)

[0106] After the temperature of wafer 200 reaches and stabilizes at the third temperature, the wafer 200, i.e., the Cl-containing Si layer and Si film formed on wafer 200, are subjected to heat treatment (annealing) within the processing chamber 201. This allows the Cl-containing Si layer and Si film to crystallize (polycrystalline). In other words, the amorphous or mixed amorphous and polycrystalline Cl-containing Si layer and Si film can be crystallized and transformed into a polycrystalline Cl-containing Si layer and Si film. This step can be performed with valves 243c, 243f, and 243g open to supply inactive gas to the processing chamber 201, or with valves 243c, 243f, and 243g closed to stop the supply of inactive gas to the processing chamber 201.

[0107] As a processing condition in step C, an example can be shown:

[0108] Inactive gas supply flow rate (each gas supply pipe): 0~20slm

[0109] Processing temperature (third temperature): 550–1000℃, preferably 600–800℃

[0110] Processing pressure: 0.1~100000Pa

[0111] Processing time: 1 to 300 minutes.

[0112] (Post-purging and atmospheric pressure recovery)

[0113] After step C, i.e., after annealing, inert gases are supplied as purge gases into the processing chamber 201 from nozzles 249a to 249c, and exhaust gases are discharged from exhaust port 231a. This purges the processing chamber 201, removing residual gases and reaction byproducts (post-purge). Then, 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 restored to atmospheric pressure (atmospheric pressure restoration).

[0114] (Crystal boat unloading and chip removal)

[0115] Then, the sealing cover 219 is lowered using the crystal boat lift 115, opening the lower end of the manifold 209. The processed wafer 200, supported by the crystal boat 217, is then moved from the lower end of the manifold 209 to the outside of the reaction tube 203 (crystal boat unloading). After unloading, the gate 219s is moved, sealing the lower opening of the manifold 209 by means of an O-ring 220c (gate closing). After being moved to the outside of the reaction tube 203, the processed wafer 200 is removed from the crystal boat 217 (wafer removal).

[0116] (3) Effects of this method

[0117] According to this method, one or more of the effects shown below can be obtained.

[0118] (a) By forming a Cl-containing Si layer at the interface (hereinafter, Si / SiO interface) between the SiO film as an insulating film and the Si film as a semiconductor film, the dangling bonds in the Si / SiO interface are capped by Cl, and their density can be controlled to decrease. Therefore, by controlling the direction of decreasing the interface state density in the Si / SiO interface, the electrical characteristics of the semiconductor device can be improved.

[0119] (b) By setting the Cl concentration of the Cl-containing Si layer to 1.0 × 10⁻⁶ 20 atoms / cm 3 Above 1.0×10 22 atoms / cm 3 The following can appropriately improve the above-mentioned effects. Furthermore, by setting the Cl concentration of the Cl-containing Si layer to 3.0 × 10⁻⁶... 20 atoms / cm 3 Above 5.0×10 21 atoms / cm 3The following methods can more appropriately enhance the aforementioned effects.

[0120] If the Cl concentration in the Cl-containing Si layer is set to be less than 1.0 × 10⁻⁶ 20 atoms / cm 3 Sometimes, Cl cannot adequately end the dangling bonds in the Si / SiO interface, thus failing to sufficiently reduce the interface state density. Consequently, the electrical characteristics of the semiconductor device may not improve. By setting the Cl concentration of the Cl-containing Si layer to 1.0 × 10⁻⁶, [the solution is achieved]. 20 atoms / cm 3 In summary, using Cl to fully end the dangling bonds at the Si / SiO interface can significantly reduce the interface state density and improve the electrical characteristics of semiconductor devices. This is achieved by setting the Cl concentration in the Cl-containing Si layer to 3.0 × 10⁻⁶. 20 atoms / cm 3 The above can further improve this effect.

[0121] If the Cl concentration in the Cl-containing Si layer is higher than 1.0 × 10⁻⁶ 22 atoms / cm 3 When the Cl concentration is excessive relative to the dangling bond density at the Si / SiO interface, Cl becomes a cause of carrier scattering, which can sometimes degrade the electrical properties of semiconductor devices. By setting the Cl concentration of the Cl-containing Si layer to 1.0 × 10⁻⁶, 22 atoms / cm 3 The following method can suppress the excessive Cl concentration relative to the dangling bond density at the Si / SiO interface, thus preventing Cl from becoming a cause of carrier scattering and suppressing the degradation of the electrical properties of semiconductor devices. This is achieved by setting the Cl concentration in the Cl-containing Si layer to 5.0 × 10⁻⁶. 21 atoms / cm 3 The following steps can further improve this effect.

[0122] (c) By setting the thickness of the Cl-containing Si layer to more than 1 mL The following method can appropriately improve the above-mentioned effect. By setting the thickness of the Cl-containing Si layer to... above The following method can more appropriately improve the above-mentioned effect. By setting the thickness of the Cl-containing Si layer to... above The following steps can further and appropriately improve the above effects.

[0123] If the thickness of the Cl-containing Si layer is less than 1 mL, the added Cl atoms at the Si / SiO interface are insufficient for the dangling bonds in the capped Si / SiO interface, failing to adequately reduce the interface state density. Consequently, the electrical characteristics of the semiconductor device may not improve. By setting the thickness of the Cl-containing Si layer to 1 mL or more, the added Cl atoms at the Si / SiO interface are sufficient for the dangling bonds in the capped Si / SiO interface, adequately reducing the interface state density and improving the electrical characteristics of the semiconductor device. The above can further improve this effect. By setting the thickness of the Cl-containing Si layer to... The above can further improve this effect.

[0124] If the thickness of the Si layer containing Cl is greater than... If the Si layer is too thick, Cl diffuses from the Cl-containing Si layer to the upper Si film, and sometimes the layer becomes too thin. Additionally, sometimes the amount of Cl at the Si / SiO interface becomes excessive. This can sometimes degrade the electrical properties of the semiconductor device. By setting the thickness of the Cl-containing Si layer as... The following method can suppress the diffusion of Cl from the Cl-containing Si layer to the upper Si film, prevent excessive Cl content at the Si / SiO interface, and suppress the degradation of the electrical properties of semiconductor devices. This is achieved by setting the thickness of the Cl-containing Si layer to... The following steps can further improve this effect.

[0125] (d) By incorporating Cl into the Si / SiO interface in the form of a Cl-containing Si layer, Cl can be precisely (locally) added only to the Si / SiO interface. This suppresses the diffusion and incorporation of Cl into the Si and SiO films, and inhibits the degradation of film properties and electrical properties caused by the incorporation of Cl into these films.

[0126] (e) By incorporating Cl into the Si / SiO interface in the form of a Cl-containing Si layer, Cl can be immobilized at the Si / SiO interface. This suppresses the diffusion of Cl from the Si / SiO interface to the adjacent film and maintains the uniformity of Cl concentration at the Si / SiO interface.

[0127] (f) In the formation of the Cl-containing Si layer, by performing steps A1 and A2 cyclically a predetermined number of times non-simultaneously, at least one of the Cl concentration and thickness of the Cl-containing Si layer can be precisely controlled. Therefore, at least one of the Cl concentration and Cl amount at the Si / SiO interface can be precisely controlled.

[0128] (g) When the above-mentioned various chlorosilane-based gases and various inactive gases are used in the formation of a Si layer containing Cl, when the above-mentioned various silane-based gases and various inactive gases are used in the formation of a Si film, and when the above-mentioned inactive gases are used in annealing, the above-mentioned effects can also be obtained.

[0129] (4) Variations

[0130] The substrate processing sequence in this method can be changed as shown in the following variations. These variations can be combined arbitrarily. Unless otherwise specified, the processing steps and conditions in each step of each variation can be the same as those in each step of the above processing sequence.

[0131] (Variation Example 1)

[0132] As shown in the substrate processing sequence below, in step A, the following steps may also be performed cyclically a predetermined number of times (n times, where n is an integer greater than or equal to 1): step A1, supplying a chlorosilane-based gas to the wafer 200 as a first gas; step A2, purging the space in which the wafer 200 exists with an inactive gas to remove the chlorosilane-based gas remaining in that space; step A3, supplying a silicon hydride gas to the wafer 200 as a third gas; and step A4, purging the space in which the wafer 200 exists with an inactive gas to remove the silicon hydride gas remaining in that space.

[0133] (chlorosilane-based gases → inactive gases → silicon hydride gases → inactive gases) × n → silane-based gases → ANL

[0134] During step A3, valve 243d is opened, allowing silicon hydride gas to flow into gas supply pipe 232d. The silicon hydride gas flow rate is regulated by MFC 241d, and it is supplied to processing chamber 201 via gas supply pipe 232a and nozzle 249a, and exhausted from exhaust port 231a. At this time, silicon hydride gas is supplied to wafer 200. At this point, valves 243c, 243f, and 243g can be opened, supplying inactive gas into processing chamber 201 via nozzles 249a to 249c respectively.

[0135] As a processing condition in step A3, the following examples can be given:

[0136] Silicon hydride gas supply flow rate: 0.1~1slm

[0137] Silicon hydride gas supply time: 0.5 to 2 minutes.

[0138] Other processing conditions can be the same as those in step A1. As the third gas (silicon hydride gas), various silicon hydride gases exemplified above as the second gas can be used.

[0139] The processing steps and conditions in step A4 can be the same as those in step A2.

[0140] The same effect as described above can be obtained through this variation. Furthermore, by performing steps A3 and A4 after steps A1 and A2, it is possible to control the direction in which the Cl concentration in the Cl-containing Si layer decreases.

[0141] (Variation Example 2)

[0142] As shown in the substrate processing sequence below, in step A, the following steps may also be performed cyclically a predetermined number of times (n times, where n is an integer greater than or equal to 1): step A1, supplying a chlorosilane-based gas to the wafer 200 as a first gas; step A2, purging the space in which the wafer 200 exists with an inactive gas to remove the chlorosilane-based gas remaining in that space; step A5, supplying an H-containing gas to the wafer 200 as a fourth gas; and step A6, purging the space in which the wafer 200 exists with an inactive gas to remove the H-containing gas remaining in that space.

[0143] (chlorosilane-based gases → inactive gases → H-containing gases → inactive gases) × n → silane-based gases → ANL

[0144] During step A5, valve 243e is opened, allowing H-containing gas to flow into gas supply pipe 232e. The H-containing gas, with flow rate regulated by MFC 241d, is supplied to processing chamber 201 via gas supply pipe 232b and nozzle 249b, and exhausted from exhaust port 231a. At this time, H-containing gas is supplied to wafer 200. Then, valves 243c, 243f, and 243g can be opened, supplying inactive gas into processing chamber 201 via nozzles 249a to 249c respectively.

[0145] As an example of the processing condition in step A5:

[0146] H-containing gas supply flow rate: 2-10 slm

[0147] H-containing gas supply time: 2-5 minutes

[0148] Processing pressure: 1333~13332Pa (10~100Torr)

[0149] Other processing conditions can be the same as those in step A1. For example, hydrogen (H2) gas can be used as the H-containing gas.

[0150] The processing steps and conditions in step A6 can be the same as those in step A2.

[0151] The same effect as described above can be obtained using this method. Furthermore, by performing step A5 after steps A1 and A2, it is possible to control the direction in which the Cl concentration in the Cl-containing Si layer decreases.

[0152] <Other ways of publishing this text>

[0153] The foregoing has provided a detailed description of the manner in which this disclosure is made. However, this disclosure is not limited to the manner described above and various changes may be made without departing from its essence.

[0154] The above method describes the case where annealing is performed after Si film formation. However, annealing may not be performed after Si film formation, as shown in the substrate processing sequence below. These cases also achieve the same effect as the method described above.

[0155] (chlorosilane-based gases → inactive gases) × n → silane-based gases

[0156] (chlorosilane-based gases → inactive gases → silicon hydride gases → inactive gases) × n → silane-based gases

[0157] (chlorosilane-based gases → inert gases → H-containing gases → inert gases) × n → silane-based gases

[0158] The above method describes the case where the semiconductor element contained in the Cl-containing semiconductor layer and semiconductor film is Si. However, the semiconductor element contained in the Cl-containing semiconductor layer and semiconductor film is not limited to Si, and may contain at least one of Si and germanium (Ge). That is, the Cl-containing semiconductor layer may contain at least one of a Cl-containing Si layer, a Cl-containing Ge layer, and a Cl-containing SiGe layer. Furthermore, the semiconductor film may contain at least one of a Si film, a Ge film, and a SiGe film. These cases also achieve the same effects as the method described above.

[0159] The above description illustrates an example of performing a series of steps from forming a Cl-containing Si layer to annealing within the same processing chamber 201 (in situ). However, this disclosure is not limited to this approach. For example, a series of steps from forming a Cl-containing Si layer to forming a Si film can be performed within the same processing chamber, followed by annealing in another processing chamber (non-in situ). This approach also yields the same effect as described above.

[0160] Alternatively, for example, other steps (other film formation) such as forming a film other than the Si film (silicon oxide film, silicon nitride film, etc.) can be performed between the formation of the Si film and annealing. In this case, a series of steps from forming the Cl-containing Si layer to annealing, including a series of other film formation steps, can be performed in the same processing chamber (first processing chamber). Alternatively, a series of steps from forming the Cl-containing Si layer to forming the Si film can be performed in the same processing chamber (first processing chamber), while a series of other film formation steps up to annealing can be performed in another processing chamber (second processing chamber). Alternatively, a series of steps from forming the Cl-containing Si layer to forming the Si film can be performed in the same processing chamber (first processing chamber), while other film formations are performed in another processing chamber (second processing chamber), and annealing is performed in yet another processing chamber (third processing chamber) or in the first processing chamber. These cases can also achieve the same effects as those described above.

[0161] In all the aforementioned scenarios, if a series of steps are performed in situ, the wafer 200 will not be exposed to the atmosphere during the process, and can be consistently processed while the wafer 200 is under vacuum. Stable substrate processing is possible. Furthermore, if some steps are performed off-site, the temperature within each processing chamber can be preset to, for example, the processing temperature of each step or a temperature close to it, reducing the time required for temperature conditioning and improving production efficiency.

[0162] The above description illustrates an example where nozzles 249a to 249c are arranged adjacent to each other, but this disclosure is not limited to this arrangement. For example, nozzles 249a and 249c may also be arranged away from nozzle 249b in a circular space between the inner wall of the reaction tube 203 and the wafer 200 (viewed from above). This arrangement will also achieve the same effect as described above.

[0163] The processes used in substrate processing are prepared individually according to the processing requirements, and preferably stored in the storage device 121c in advance via an electrical communication line and an external storage device 123. Furthermore, at the start of processing, it is preferable that the CPU 121a appropriately selects a suitable process from among the multiple processes stored in the storage device 121c based on the substrate processing requirements. This allows for the reproducible formation of films of various types, compositions, qualities, and thicknesses within a single substrate processing apparatus. Additionally, it reduces operator workload, avoids operational errors, and enables rapid initiation of each processing step.

[0164] The aforementioned process is not limited to newly manufactured cases; for example, it can also be prepared by modifying an existing process already installed in the substrate processing apparatus. In the case of process modification, the modified process can also be installed in the substrate processing apparatus via an electrical communication line and a recording medium containing the modified process. Alternatively, the input / output device 122 of an existing substrate processing apparatus can be operated to directly modify the existing process already installed in the substrate processing apparatus.

[0165] The above method describes an example of forming a film using a batch substrate processing apparatus that processes multiple substrates at a time. This disclosure is not limited to the above method; for example, it can also be suitably applied when forming a film using a monolithic substrate processing apparatus that processes one or several substrates at a time. Furthermore, the above method describes an example of forming a film using a substrate processing apparatus with a hot-wall type furnace. This disclosure is not limited to the above method; it can also be suitably applied when forming a film using a substrate processing apparatus with a cold-wall type furnace.

[0166] When using these substrate processing devices, film formation can be performed in the same order and under the same processing conditions as described above and in the modified examples, and the same effects can be obtained.

[0167] Furthermore, the above methods and variations can be used in appropriate combinations. In this case, the processing steps and conditions can be the same as those in the methods described above.

[0168] Example

[0169] use Figure 1 The substrate processing apparatus shown utilizes Figure 4 The substrate processing sequence shown involves sequentially forming a Cl-containing Si layer and a Si film on a SiO film disposed on the surface of the wafer to prepare evaluation samples. The processing steps and conditions in each step are the same as those in the steps described above. Multiple samples are prepared as evaluation samples, in which the Cl concentration in the Cl-containing Si layer is varied. Furthermore, the dangling bond density in each evaluation sample is measured.

[0170] Figure 5 The figure shows the relationship between Cl concentration and dangling bond density at the interface between the Si film and the SiO film (hereinafter, Si / SiO interface) of each evaluation sample, i.e., the dependence of dangling bond density on Cl concentration at the Si / SiO interface. Figure 5 The horizontal axis represents the Cl concentration at the Si / SiO interface [atoms / cm]. 3 The vertical axis represents the density of dangling bonds at the Si / SiO interface [number / cm²]. 3The ● mark in the figure indicates the results obtained by plotting the measured values ​​of dangling bond density in each evaluation sample.

[0171] according to Figure 5 It is known that the higher the Cl concentration at the Si / SiO interface, the lower the dangling bond density. In particular, by setting the Cl concentration at the Si / SiO interface to 1.0 × 10⁻⁶... 20 atoms / cm 3 The preferred value is set to 3.0 × 10. 20 atoms / cm 3 The above methods can significantly reduce the density of dangling bonds.

[0172] Explanation of reference numerals in the attached figures

[0173] 200 wafers (substrates)

Claims

1. A substrate processing method, which has the following characteristics: (a) The step of supplying a first gas containing a semiconductor element and chlorine to a substrate, and forming a chlorine-containing semiconductor layer on a chlorine-free insulating film disposed on the surface of the substrate; and (b) The step of supplying a second gas containing a semiconductor element to the substrate to form a chlorine-free semiconductor film on the chlorine-containing semiconductor layer. The chlorine concentration of the chlorine-containing semiconductor layer formed in (a) is set to 1.0 × 10⁻⁶. 20 atoms / cm 3 Above 1.0×10 22 atoms / cm 3 the following.

2. The substrate processing method as described in claim 1, wherein, The chlorine concentration of the chlorine-containing semiconductor layer formed in (a) is set to 3.0 × 10⁻⁶. 20 atoms / cm 3 Above 5.0×10 21 atoms / cm 3 the following.

3. The substrate processing method as described in claim 1, wherein, The thickness of the chlorine-containing semiconductor layer formed in (a) is set to more than one monolayer and less than 30 Å.

4. The substrate processing method as described in claim 1, wherein, The thickness of the chlorine-containing semiconductor layer formed in (a) is set to be more than 2.5 Å and less than 30 Å.

5. The substrate processing method as described in claim 1, wherein, The thickness of the chlorine-containing semiconductor layer formed in (a) is set to be more than 3 Å and less than 20 Å.

6. The substrate processing method as described in claim 1, wherein, In (a), the following steps will be performed cyclically a predetermined number of times: (a1) a step of supplying the first gas to the substrate; and (a2) a step of removing the first gas remaining in the space where the substrate exists.

7. The substrate processing method as described in claim 1, wherein, In (a), the following steps are performed cyclically a predetermined number of times: (a1) a step of supplying the first gas to the substrate; (a2) a step of removing the first gas remaining in the space where the substrate exists; (a3) ​​a step of supplying the third gas containing semiconductor elements and hydrogen to the substrate; and (a4) a step of removing the third gas remaining in the space where the substrate exists.

8. The substrate processing method as described in claim 6 or 7, wherein, The chlorine concentration at the interface between the insulating film and the semiconductor film is controlled by one or more of the following: the temperature of the substrate, the pressure of the space in which the substrate exists, the supply flow rate of the first gas, and the supply time of the first gas.

9. The substrate processing method as described in claim 6 or 7, wherein, The chlorine concentration at the interface between the insulating film and the semiconductor film is controlled by the number of cycles described in (a).

10. The substrate processing method as described in claim 6 or 7, wherein, The dangling bond density at the interface between the insulating film and the semiconductor film is controlled by one or more of the following: the temperature of the substrate, the pressure of the space in which the substrate exists, the supply flow rate of the first gas, and the supply time of the first gas.

11. The substrate processing method as described in claim 6 or 7, wherein, The density of dangling bonds at the interface between the insulating film and the semiconductor film is controlled by the number of cycles.

12. The substrate processing method as described in claim 1, wherein, The thickness of the chlorine-containing semiconductor layer is made thinner than the thickness of the insulating film and the semiconductor film, respectively.

13. The substrate processing method as described in claim 1, wherein, The chlorine-containing semiconductor layer forms the interface between the insulating film and the semiconductor film.

14. The substrate processing method as described in claim 1, wherein, The semiconductor element includes at least one of silicon and germanium.

15. The substrate processing method as described in claim 1, wherein, The chlorine-containing semiconductor layer comprises at least one of a chlorine-containing silicon layer, a chlorine-containing germanium layer, and a chlorine-containing silicon-germanium layer. The semiconductor film includes at least one of a silicon film, a germanium film, and a silicon-germanium film.

16. The substrate processing method according to claim 1, further comprising: (c) a step of annealing the substrate after the semiconductor film is formed on the chlorine-containing semiconductor layer.

17. The substrate processing method as described in claim 16, wherein, In the annealing process, the chlorine-containing semiconductor layer and the semiconductor film are crystallized.

18. A method for manufacturing a semiconductor device, comprising: (a) The step of supplying a first gas containing a semiconductor element and chlorine to a substrate, and forming a chlorine-containing semiconductor layer on a chlorine-free insulating film disposed on the surface of the substrate; and (b) The step of supplying a second gas containing a semiconductor element to the substrate to form a chlorine-free semiconductor film on the chlorine-containing semiconductor layer. The chlorine concentration of the chlorine-containing semiconductor layer formed in (a) is set to 1.0 × 10⁻⁶. 20 atoms / cm 3 Above 1.0×10 22 atoms / cm 3 the following.

19. A substrate processing apparatus, comprising: A first gas supply system supplies a first gas containing semiconductor elements and chlorine to the substrate; A second gas supply system supplies a second gas containing semiconductor elements to the substrate; and The control unit is configured to set the chlorine concentration of the chlorine-containing semiconductor layer formed in (a) to 1.0 × 10⁻⁶ by performing the following process. 20 atoms / cm 3 Above 1.0×10 22 atoms / cm 3 The first gas supply system and the second gas supply system are controlled in the following manner: (a) A process of supplying the first gas to a substrate to form a chlorine-containing semiconductor layer on a chlorine-free insulating film disposed on the surface of the substrate; and (b) A process of supplying the second gas to the substrate to form a chlorine-free semiconductor film on the chlorine-containing semiconductor layer.

20. A computer-readable recording medium having a program recorded thereon that enables a substrate processing apparatus to perform the following steps using a computer: (a) The step of supplying a first gas containing a semiconductor element and chlorine to a substrate to form a chlorine-containing semiconductor layer on a chlorine-free insulating film disposed on the surface of the substrate; (b) The step of supplying a second gas containing a semiconductor element to the substrate to form a chlorine-free semiconductor film on the chlorine-containing semiconductor layer; and The chlorine concentration of the chlorine-containing semiconductor layer formed in (a) is set to 1.0 × 10⁻⁶. 20 atoms / cm 3 Above 1.0×10 22 atoms / cm 3 The following steps.

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