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

Abstract

The present invention has a step for forming a film containing a first element, a second element, carbon, and a halogen on a substrate by performing a cycle including steps (a) and (b) a predetermined number of times; the step (a) is a step for supplying a raw material to the substrate, said raw material containing the first element, carbon, and halogen and not containing a chemical bond between carbon and hydrogen. The step (b) is a step for supplying a reaction body containing the second element different from the first element to the substrate.

Description

Technical Field

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

[0002] As one of the steps in the process of manufacturing a semiconductor device, a process of forming a film on a substrate is sometimes performed (see, for example, Patent Documents 1 and 2).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2017 / 046921 Pamphlet

[0006] Patent Document 2: Japanese Patent Application Publication No. 2014-183218 Summary of the invention

[0007] Problems to be solved by the invention

[0008] As semiconductor devices become smaller, there is a strong demand for improving the film quality of films formed on substrates.

[0009] The present invention provides a technology capable of improving the film quality of a film formed on a substrate.

[0010] Solution to the problem

[0011] According to one embodiment of the present invention, there is provided a technique for forming a film containing a first element, a second element, carbon, and a halogen on a substrate by performing a cycle including the following steps (a) and (b) a predetermined number of times;

[0012] (a) supplying a raw material containing the first element, carbon and halogen and not containing a chemical bond between carbon and hydrogen to the substrate;

[0013] (b) A step of supplying a reactant containing the second element different from the first element to the substrate.

[0014] Effects of the Invention

[0015] According to the present invention, the film quality of a film formed on a substrate can be improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a schematic diagram of the structure of a vertical processing furnace of a substrate processing apparatus that is preferably used in one embodiment of the present invention, and is a diagram showing a processing furnace 202 portion in a longitudinal cross-sectional view.

[0017] Figure 2The schematic diagram of a vertical processing furnace of a substrate processing device suitable for use in one embodiment of the present invention is shown in FIG. Figure 1 The AA line cross-sectional view shows a portion of the processing furnace 202 .

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

[0019] Figure 4 It is a diagram showing a substrate processing flow in one embodiment of the present invention.

[0020] Figure 5 In the figure, (a) is a diagram showing an example of a partial structure of a molecule of a raw material in one embodiment of the present invention, and (b) is a diagram showing another example of a partial structure of a molecule of a raw material in one embodiment of the present invention. DETAILED DESCRIPTION

[0021] <One embodiment of the present invention>

[0022] The following mainly refers to Figures 1 to 4 , Figure 5 (a) Figure 5 (b) One embodiment of the present invention is described. It should be noted that the drawings used in the following description are schematic drawings, and the dimensional relationship of each element, the ratio of each element, etc. shown in the drawings may not be consistent with the actual ones. In addition, the dimensional relationship of each element, the ratio of each element, etc. between multiple drawings may not be consistent.

[0023] (1) Configuration of substrate processing apparatus

[0024] like Figure 1 As shown, the processing furnace 202 has a heater 207 as a temperature adjuster (heating unit). The heater 207 is cylindrical and is vertically installed by being supported by a holding plate. The heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) the gas using heat.

[0025] On the inner side of 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 an upper end and a lower end open. The upper end of the manifold 209 is engaged with the lower end of the reaction tube 203, and is configured to support the reaction tube 203. An O-ring 220a as a sealing member is provided between the manifold 209 and the reaction tube 203. The reaction tube 203 is installed vertically in the same manner as the heater 207. The reaction tube 203 and the manifold 209 mainly constitute a processing container (reaction container). The processing chamber 201 is formed in the hollow portion of the cylinder of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. The wafer 200 is processed in the processing chamber 201 .

[0026] Nozzles 249a to 249c as first to third supply parts are respectively arranged in the processing chamber 201 in a manner penetrating the side wall of the manifold 209. The nozzles 249a to 249c are also referred to as first to third nozzles, respectively. The nozzles 249a to 249c are made of, for example, a heat-resistant material such as quartz or SiC. The nozzles 249a to 249c are respectively connected to the gas supply pipes 232a to 232c. The nozzles 249a to 249c are different nozzles, and the nozzles 249a and 249c are respectively arranged adjacent to the nozzle 249b.

[0027] In the gas supply pipes 232a to 232c, mass flow controllers (MFC) 241a to 241c as flow controllers (flow control units) and valves 243a to 243c as opening and closing valves are respectively provided in order from the upstream side of the gas flow. A gas supply pipe 232d is connected to the gas supply pipe 232a on the downstream side of the valve 243a. A gas supply pipe 232e is connected to the gas supply pipe 232b on the downstream side of the valve 243b. A gas supply pipe 232f is connected to the gas supply pipe 232c on the downstream side of the valve 243c. In the gas supply pipes 232d to 232f, MFCs 241d to 241f and valves 243d to 243f are respectively provided in order from the upstream side of the gas flow. The gas supply pipes 232a to 232f are made of metal materials such as SUS, for example.

[0028] like Figure 2As shown, in the annular space between the inner wall of the reaction tube 203 and the wafer 200 when viewed from above, nozzles 249a to 249c are respectively arranged from the lower part of the inner wall of the reaction tube 203 along the upper part in a manner of standing upward in the arrangement direction of the wafer 200. That is, in the area horizontally surrounding the wafer arrangement area on the side of the wafer arrangement area where the wafers 200 are arranged, the nozzles 249a to 249c are respectively arranged along the wafer arrangement area. When viewed from above, the nozzle 249b is arranged in a manner of facing the exhaust port 231a described later on a straight line across the center of the wafer 200 carried into the processing chamber 201. The nozzles 249a and 249c are arranged in a manner of sandwiching a straight line L passing through the center of the nozzle 249b and the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer periphery of the wafer 200). The straight line L is also a straight line passing through the nozzle 249b and the center of the wafer 200. That is, the nozzle 249c may also be provided on the opposite side of the nozzle 249a across the straight line L. The nozzles 249a and 249c are arranged line-symmetrically with the straight line L as the axis of symmetry. Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. The gas supply holes 250a to 250c are opened in a manner opposite (facing) to the exhaust port 231a when viewed from above and are capable of supplying gas toward the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the bottom to the top of the reaction tube 203.

[0029] The raw material is supplied from the gas supply pipe 232a through the MFC 241a, the valve 243a, and the nozzle 249a into the processing chamber 201. The raw material is used as one of the film-forming agents.

[0030] The reactant is supplied from the gas supply pipe 232b through the MFC 241b, the valve 243b, and the nozzle 249b into the processing chamber 201. The reactant is used as one of the film-forming agents.

[0031] The catalyst is supplied from the gas supply pipe 232c through the MFC 241c, the valve 243c, the gas supply pipe 232c, and the nozzle 249c into the processing chamber 201. The catalyst is used as one of the film-forming agents.

[0032] The inert gas is supplied from the gas supply pipes 232d to 232f through the MFCs 232d to 241f, valves 243d to 243f, gas supply pipes 232a to 232c, and nozzles 249a to 249c into the processing chamber 201. The inert gas is used as a purge gas, a carrier gas, a dilution gas, and the like.

[0033] The raw material supply system is mainly composed of the gas supply pipe 232a, MFC241a, and valve 243a. The reactant supply system is mainly composed of the gas supply pipe 232b, MFC241b, and valve 243b. The catalyst supply system is mainly composed of the gas supply pipe 232c, MFC241c, and valve 243c. The inert gas supply system is mainly composed of the gas supply pipes 232d to 232f, MFC232d to 241f, and valves 243d to 243f. The raw material supply system, the reactant supply system, and the catalyst supply system are also individually or collectively referred to as the film forming agent supply system.

[0034] Among the various supply systems described above, any one or all of the supply systems may be configured as an integrated supply system 248 formed by integrating valves 243a to 243f, MFCs 241a to 241f, etc. The integrated supply system 248 is connected to the gas supply pipes 232a to 232f, respectively, and is configured to control the supply operation of various substances (various gases) in the gas supply pipes 232a to 232f, that is, the opening and closing operation of the valves 243a to 243f, the flow rate adjustment operation of the MFCs 241a to 241f, etc., through the controller 121 described later. The integrated supply system 248 is configured as an integrated unit of an integral type or a split type, and the gas supply pipes 232a to 232f, etc. can be loaded and unloaded as an integrated unit unit, and is configured to be able to perform maintenance, replacement, and additional installation of the integrated supply system 248 as an integrated unit unit.

[0035] An exhaust port 231a is provided below the side wall of the reaction tube 203 to exhaust the atmosphere in the processing chamber 201. Figure 2 As shown, the exhaust port 231a is arranged at a position opposite (facing) the nozzles 249a to 249c (gas supply holes 250a to 250c) across the wafer 200 when viewed from above. The exhaust port 231a can also be arranged from the lower part of the side wall of the reaction tube 203 along the upper part, that is, along the wafer arrangement area. The exhaust port 231a is connected to the exhaust pipe 231. The exhaust pipe 231 is connected to a vacuum pump 246 as a vacuum exhaust device via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an automatic pressure controller (APC, Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit). The APC valve 244 is configured to open and close the valve while the vacuum pump 246 is in operation, thereby performing vacuum exhaust and stopping vacuum exhaust in the processing chamber 201. Furthermore, the pressure in the processing chamber 201 can be adjusted by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is in operation. The exhaust system is mainly composed of the exhaust pipe 231, the APC valve 244, and the pressure sensor 245. The vacuum pump 246 may also be included in the exhaust system.

[0036] Below the manifold 209, a sealing cover 219 as a furnace cover body capable of hermetically sealing the lower end opening of the manifold 209 is provided. 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 as a sealing member abutting against the lower end of the manifold 209 is provided. Below the sealing cover 219, a rotating mechanism 267 for rotating the wafer box 217 described later is provided. The rotating shaft 255 of the rotating mechanism 267 passes through the sealing cover 219 and is connected to the wafer box 217. The rotating mechanism 267 is configured to rotate the wafer 200 by rotating the wafer box 217. The sealing cover 219 is configured to be lifted and lowered in the vertical direction by the wafer box elevator 115 as a lifting mechanism provided outside the reaction tube 203. The cassette elevator 115 is configured as a transport device (transport mechanism) that carries the wafer 200 in and out (transports) 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 baffle 219s is provided as a furnace cover body that can hermetically seal the lower end opening of the manifold 209 when the sealing cover 219 is lowered and the wafer box 217 is carried out from the processing chamber 201. The baffle 219s is made of a metal material such as SUS and is formed in a disc shape. An O-ring 220c is provided on the upper surface of the baffle 219s as a sealing member that abuts against the lower end of the manifold 209. The opening and closing action (lifting action or rotation action, etc.) of the baffle 219s is controlled by the baffle opening and closing mechanism 115s.

[0038] The wafer box 217 as a substrate support is configured to support multiple (e.g., 25 to 200) wafers 200 in a horizontal position and with their centers aligned with each other in a vertical direction in multiple stages, that is, arranged at intervals. The wafer box 217 is made of, for example, a heat-resistant material such as quartz or SiC. At the bottom of the wafer box 217, a heat insulation plate 218 made of, for example, a heat-resistant material such as quartz or SiC is supported in multiple stages.

[0039] A temperature sensor 263 as a temperature detector is provided in the reaction tube 203. The degree of energization of the heater 207 is adjusted based on temperature information detected by the temperature sensor 263, so that the temperature in the processing chamber 201 has a desired temperature distribution. The temperature sensor 263 is provided along the inner wall of the reaction tube 203.

[0040] like Figure 3As shown, the controller 121 as a control unit (control means) is configured as a computer having a central processing unit (CPU) 121a, a random access memory (RAM) 121b, a storage device 121c, and an I / O interface 121d. The RAM 121b, the storage device 121c, and the I / O interface 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e. The controller 121 is connected to an input / output device 122 such as a touch panel. In addition, the controller 121 can be connected to an external storage device 123.

[0041] The storage device 121c is composed of, for example, a flash memory, a hard disk drive (HDD), a solid state drive (SSD), etc. In the storage device 121c, a control program for controlling the actions of the substrate processing device, a process recipe that records the process and conditions of the substrate processing described later, etc. can be read and recorded and stored. The process recipe is a combination of the substrate processing device to execute each process in the substrate processing described later and obtain a specified result through the controller 121, and functions as a program. Hereinafter, the process recipe, control program, etc. are also collectively referred to as programs. In addition, the process recipe is also referred to as a recipe. When the term program is used in this specification, there is a case where only a recipe body is included, a case where only a control program body is included, or a case where both are included. RAM121b is configured as a storage area (working area) for temporarily storing programs, data, etc. read by CPU121a.

[0042] The I / O interface 121d is connected to the above-mentioned MFCs 241a to 241f, valves 243a to 243f, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, wafer box elevator 115, shutter opening and closing mechanism 115s, etc.

[0043] The CPU 121a is configured to read a control program from the storage device 121c and execute it, and can read a recipe from the storage device 121c according to 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 recipe, flow rate adjustment operations of various substances (various gases) by the MFCs 241a to 241f, opening and closing operations of the valves 243a to 243f, opening and closing operations of the APC valve 244 and pressure adjustment operations by the APC valve 244 based on the pressure sensor 245, start and stop of the vacuum pump 246, temperature adjustment operations of the heater 207 based on the temperature sensor 263, rotation of the wafer cassette 217 and rotation speed adjustment operations by the rotation mechanism 267, lifting and lowering operations of the wafer cassette 217 by the wafer cassette elevator 115, opening and closing operations of the shutter 219s by the shutter opening and closing mechanism 115s, and the like.

[0044] The controller 121 can be configured by installing the above-mentioned program recorded and stored in the external storage device 123 on a computer. The external storage device 123 includes, for example, magnetic disks such as HDD, optical disks such as CD, magneto-optical disks such as MO, USB memory, semiconductor memory such as SSD, etc. The storage device 121c and the external storage device 123 are configured as a recording medium that can be read by a computer. Hereinafter, they are also collectively referred to as recording media. When the term recording medium is used in this specification, there is a case where only the storage device 121c monomer is included, a case where only the external storage device 123 monomer is included, or a case where both are included. It should be noted that the provision of the program to the computer can also be carried out without using the external storage device 123, but using a communication unit such as the Internet or a dedicated line.

[0045] (2) Substrate processing steps

[0046] As one of the steps in the manufacturing process of a semiconductor device using the substrate processing apparatus, a Figure 4 , Figure 5 (a) Figure 5 (b) A method of processing a substrate, that is, an example of a process flow for forming a film on a wafer 200 as a substrate will be described. In the following description, the operations of the various components constituting the substrate processing apparatus are controlled by the controller 121 .

[0047] In the processing flow of this method, a step (film forming step) of forming a film containing a first element, a second element, carbon and a halogen on a wafer 200 is performed by performing a cycle including step (a) and step (b) a predetermined number of times (n times, n is an integer greater than 1); the above step (a) is a step of supplying a raw material containing the first element, carbon and a halogen and not containing a chemical bond between carbon and hydrogen to the wafer 200 (raw material supply step), and the above step (b) is a step of supplying a reactant containing a second element different from the above first element to the wafer 200 (reactant supply step). Each step is performed in a non-plasma atmosphere.

[0048] In addition, in the following example, Figure 4 As shown in FIG. 1 , a case where a catalyst is further supplied to the wafer 200 in at least one of the raw material supplying step and the reactant supplying step will be described. Figure 4 , as a representative example, an example in which a catalyst is further supplied to the wafer 200 in both the raw material supply step and the reactant supply step is shown.

[0049] In this specification, for the sake of convenience, the above-mentioned processing flow may be expressed as follows. The same expression is also used in the following description of the modified examples or other aspects.

[0050] (Raw material + catalyst → Reactant + catalyst) × n

[0051] It should be noted that, as in the following process flow, a catalyst may be further supplied to the wafer 200 in at least one of the raw material supplying step and the reactant supplying step.

[0052] (Raw material + catalyst → reactant) × n

[0053] (Raw material → Reactant + Catalyst) × n

[0054] (Raw material + catalyst → Reactant + catalyst) × n

[0055] In addition, if Figure 4 Alternatively, as in the following process flow, after the film forming step, a step of heat-treating the wafer 200 (heat-treating step) may be further performed.

[0056] (Raw material + catalyst → reactant) × n → heat treatment

[0057] (Raw material → Reactant + Catalyst) × n → Heat treatment

[0058] (raw material + catalyst → reactant + catalyst) × n → heat treatment

[0059] The term "wafer" used in this specification may refer to the wafer itself or to a laminate of a wafer and a predetermined layer or film formed on its surface. The term "surface of the wafer" used in this specification may refer to the surface of the wafer itself or to the surface of a predetermined layer, etc. formed on the wafer. When it is stated in this specification that "a predetermined layer is formed on the wafer", it means that a predetermined layer is directly formed on the surface of the wafer itself or that a predetermined layer is formed on a layer, etc. formed on the wafer. When the term "substrate" is used in this specification, it has the same meaning as when the term "wafer" is used.

[0060] The term "agent" used in this specification includes at least one of a gaseous substance and a liquid substance. A liquid substance includes a mist substance. That is, a film-forming agent (raw material, reactant, catalyst) may include a gaseous substance, a liquid substance such as a mist substance, or both.

[0061] The term "layer" used in this specification includes at least one of a continuous layer and a discontinuous layer. The layer formed in each step described below may include a continuous layer, a discontinuous layer, or both.

[0062] (Wafer loading and wafer box loading)

[0063] When a plurality of wafers 200 are loaded into the wafer box 217 (wafer loading), the shutter 219s is moved by the shutter opening and closing mechanism 115s to open the lower end opening of the manifold 209 (shutter opening). 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 (wafer cassette loading). In this state, the sealing cap 219 seals the lower end of the manifold 209 via the O-ring 220b. In this way, the wafers 200 are prepared in the processing chamber 201.

[0064] (Pressure adjustment and temperature adjustment)

[0065] After the wafer box is loaded, vacuum exhaust (decompression exhaust) is performed by the vacuum pump 246 so that the space in the processing chamber 201, that is, the space where the wafer 200 is located, becomes the required pressure (vacuum degree). At this time, the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information. In addition, the heater 207 is used to heat the wafer 200 in the processing chamber 201 so that it reaches the required processing temperature. At this time, the degree of power supply to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 in such a way that the processing chamber 201 reaches the required temperature distribution. In addition, the rotation of the wafer 200 is started by the rotating mechanism 267. The exhaust in the processing chamber 201, the heating and rotation of the wafer 200 are all continued until at least the processing of the wafer 200 is completed.

[0066] (Film Forming Step)

[0067] Then, the following raw material supply step and reactant supply step are performed in order.

[0068] [Raw material supply step]

[0069] In this step, a raw material (raw material gas) and a catalyst (catalyst gas) serving as a film-forming agent are supplied to the wafer 200 .

[0070] Specifically, valves 243a and 243c are opened, and raw materials and catalysts are circulated in gas supply pipes 232a and 232c, respectively. The raw materials and catalysts are adjusted in flow rate by MFC241a and 241c, respectively, and supplied to the processing chamber 201 through nozzles 249a and 249c, mixed in the processing chamber 201, and exhausted from the exhaust port 231a. At this time, raw materials and catalysts are supplied to the wafer 200 from the side of the wafer 200 (supply of raw materials + catalysts). At this time, valves 243d to 243f can also be opened to supply inactive gases to the processing chamber 201 through nozzles 249a to 249c, respectively.

[0071] By supplying a raw material and a catalyst to the wafer 200 under the processing conditions described later, the first layer is formed on the wafer 200. The first layer is a layer containing the first element, carbon, and halogen.

[0072] In this step, by supplying a catalyst together with the raw material, the above reaction can be carried out in a non-plasma atmosphere and under relatively low temperature conditions as described later. Thus, thermal decomposition (gas phase decomposition), that is, self-decomposition, of the raw material in the processing chamber 201 can be suppressed, and when the above reaction is carried out, at least a part of the chemical bonds in the raw material can be maintained without being cut, and at least a part of the partial structure of the molecules of the raw material can be maintained without being destroyed. The first layer becomes a layer containing at least a part of the chemical bonds in the raw material and at least a part of the partial structure of the molecules of the raw material.

[0073] It should be noted that since the raw material used in this step does not contain a chemical bond between carbon and hydrogen, the first layer is a layer that substantially does not contain a chemical bond between carbon and hydrogen, that is, a layer that does not contain a chemical bond between carbon and hydrogen.

[0074] As the treatment conditions when supplying the raw material and the catalyst in the raw material supply step, the following can be exemplified:

[0075] Treatment temperature: room temperature (25°C) to 200°C, preferably room temperature to 150°C,

[0076] Processing pressure: 133~1333Pa,

[0077] Raw material supply flow rate: 0.001~2slm,

[0078] Catalyst supply flow rate: 0.001~2slm,

[0079] Inert gas supply flow rate (per gas supply pipe): 0~20slm,

[0080] Each gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds.

[0081] It should be noted that the expression of a numerical range such as "133-1333Pa" in this specification means that the range includes a lower limit and an upper limit. Therefore, for example, the so-called "133-1333Pa" means "above 133Pa and below 1333Pa". The same applies to other numerical ranges. In addition, the so-called processing temperature in this specification refers to the temperature of the wafer 200 or the temperature in the processing chamber 201, and the so-called processing pressure refers to the pressure in the processing chamber 201. In addition, the so-called processing time refers to the time during which the processing continues. In addition, when the supply flow rate includes 0slm, the so-called 0slm refers to a situation where the substance (gas) is not supplied. These are also the same in the following descriptions.

[0082] After the first layer is formed on the wafer 200, the valves 243a and 243c are closed to stop the supply of raw materials and catalysts into the processing chamber 201. Then, the processing chamber 201 is evacuated to remove gaseous substances remaining in the processing chamber 201 from the processing chamber 201. At this time, the valves 243d to 243f are opened to supply inert gas into the processing chamber 201 through the nozzles 249a to 249c. The inert gas supplied by the nozzles 249a to 249c acts as a purge gas, thereby purging (scavenging) the processing chamber 201. The processing temperature during the purge in this step is preferably set to the same temperature as the processing temperature during the supply of the raw materials and catalysts.

[0083] As a raw material, for example, a substance containing a first element, carbon (C) and a halogen and not containing a chemical bond between carbon (C) and hydrogen (H) can be used. The first element includes, for example, silicon (Si). Halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc.

[0084] The raw material may contain a chemical bond between the first element and carbon and a chemical bond between a halogen and carbon. By using such a substance as the raw material, the first layer can contain these chemical bonds in the raw material, that is, the chemical bond between the first element and carbon and the chemical bond between the halogen and carbon.

[0085] The molecule of the raw material may also include a partial structure in which at least two of the four bonds of the carbon atom are respectively bonded to halogen atoms, and the remaining bonds are respectively bonded to atoms of the first element.

[0086] For example, Figure 5 As shown in (a), the molecule of the raw material may also include a partial structure in which two of the four bonds of the carbon (C) atom are respectively bonded to the halogen (X) atom and the remaining two bonds are respectively bonded to the atom of the first element. Figure 5 As shown in (b), the molecule of the raw material may also include a partial structure in which three of the four bonds of the carbon (C) atom are respectively bonded to atoms of the halogen (X) and the remaining one is bonded to an atom of the first element.

[0087] By using such a substance as a raw material, the first layer can contain the above-mentioned partial structure, that is, Figure 5 (a) Figure 5 (b) Partial structure shown.

[0088] As the raw material, for example, bistrichlorosilane difluoromethane (Cl3Si-CF2-SiCl3), bistrichlorosilane dichloromethane (Cl3Si-CCl2-SiCl3), trifluoromethyltrichlorosilane (Cl3Si-CF3), and trichloromethyltrichlorosilane (Cl3Si-CCl3) can be used.

[0089] Cl3Si-CF2-SiCl3 contains Si, C, F and Cl, does not contain CH bonds, contains Si-C-Si bonds and FC bonds. The molecule contains Figure 5 (a) is a partial structure of the type shown, that is, a partial structure (Si-CF2-Si) in which two of the four chemical bonds of C located at the center of the Si-C-Si bond are respectively bonded to F and the remaining two chemical bonds are respectively bonded to Si. By using such a substance as a raw material, a layer containing Si and C and containing F as a halogen but not containing a CH bond can be formed as the first layer. In addition, the first layer can contain chemical bonds in the raw material (Si-C-Si bonds, FC bonds) and a partial structure of the raw material molecule (Si-CF2-Si).

[0090] Cl3Si-CCl2-SiCl3 contains Si, C and Cl, does not contain CH bonds, contains Si-C-Si bonds and Cl-C bonds. The molecule contains Figure 5 (a) is a partial structure of the type shown, that is, a partial structure (Si-CCl2-Si) in which, among the four chemical bonds of C located at the center of the Si-C-Si bond, two chemical bonds are respectively bonded to Cl and the remaining two chemical bonds are respectively bonded to Si. By using such a substance as a raw material, a layer containing Si and C and containing Cl as a halogen but not containing a CH bond can be formed as the first layer. In addition, the first layer can contain the chemical bonds in the raw material (Si-C-Si bond, Cl-C bond) and the partial structure of the raw material molecule (Si-CCl2-Si).

[0091] Cl3Si-CF3 contains Si, C, F and Cl, does not contain CH bonds, contains Si-C bonds and FC bonds. Figure 5 (b) A partial structure of the type shown, that is, a partial structure (Si-CF3) in which three of the four chemical bonds of C contained in the Si-C bond are respectively bonded to F and the remaining one is bonded to Si. By using such a substance as a raw material, a layer containing Si and C and containing F as a halogen but not containing a CH bond can be formed as the first layer. In addition, the first layer can contain chemical bonds (Si-C bonds, FC bonds) in the raw material and contain a partial structure of the raw material molecule (Si-CF3).

[0092] Cl3Si-CCl3 contains Si, C and Cl, does not contain CH bonds, contains Si-C bonds and Cl-C bonds. Figure 5 (b) A partial structure of the type shown, that is, a partial structure (Si-CCl3) in which three of the four chemical bonds of C contained in the Si-C bond are respectively bonded to Cl and the remaining one chemical bond is bonded to Si. By using such a substance as a raw material, a layer containing Si and C and containing Cl as a halogen but not containing a CH bond can be formed as the first layer. In addition, the first layer can contain the chemical bonds in the raw material (Si-C bonds, Cl-C bonds) and contain the partial structure of the raw material molecule (Si-CCl3).

[0093] As raw materials, one or more of these can be used. It should be noted that, among these substances exemplified as raw materials, the remaining three bonds that are not combined with C in the four bonds of Si contained in the partial structure of the raw material molecule are all combined with Cl, but the raw materials that can be used in the present invention are not limited to these substances. That is, at least any one of the remaining three bonds that are not combined with C in the four bonds of Si contained in the partial structure can also be combined with a halogen other than Cl (F, etc.), and in addition, elements other than halogen (H, etc.) can also be combined.

[0094] As a catalyst, for example, an amine gas (amine substance) containing carbon (C), nitrogen (N) and hydrogen (H) can be used. As an amine gas (amine substance), a cyclic amine gas (cyclic amine substance) or a chain amine gas (chain amine substance) can be used. As a catalyst, for example, pyridine (C5H5N), aminopyridine (C5H6N2), methylpyridine (C6H7N), dimethylpyridine (C7H9N), pyrimidine (C4H4N2), quinoline (C9H7N), piperazine (C4H 10 N2), piperidine (C5H 11 N), cyclic amines such as aniline (C6H7N). In addition, as a catalyst, for example, triethylamine ((C2H5)3N, abbreviated as TEA), diethylamine ((C2H5)2NH, abbreviated as DEA), monoethylamine ((C2H5)NH2, abbreviated as MEA), trimethylamine ((CH3)3N, abbreviated as TMA), dimethylamine ((CH3)2NH, abbreviated as DMA), monomethylamine ((CH3)NH2, abbreviated as MMA) and the like chain amines can be used. As a catalyst, one or more of these can be used. This aspect is also the same in the reactant supply step described later.

[0095] As the inert gas, inert gases such as nitrogen (N2) gas, argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas can be used. As the inert gas, one or more of these can be used. This aspect is also the same in each step described later.

[0096] [Reactant supply step]

[0097] After the raw material supply step is completed, a reactant (reaction gas) and a catalyst (catalyst gas) as a film-forming agent are supplied to the wafer 200, that is, the wafer 200 after the first layer is formed. Here, an example of using an oxidant (oxidizing gas) containing oxygen as a second element different from the first element as the reactant (reaction gas) is described.

[0098] Specifically, valves 243b and 243c are opened, and reactants and catalysts are circulated in gas supply pipes 232b and 232c, respectively. The reactants and catalysts are adjusted in flow rate by MFC241b and 241c, respectively, and supplied to the processing chamber 201 through nozzles 249b and 249c, mixed in the processing chamber 201, and exhausted from the exhaust port 231a. At this time, reactants and catalysts are supplied to the wafer 200 from the side of the wafer 200 (supply of reactants + catalysts). At this time, valves 243d~243f can also be opened to supply inactive gases to the processing chamber 201 through nozzles 249a~249c, respectively.

[0099] By supplying a reactant and a catalyst to the wafer 200 under the processing conditions described later, at least a portion of the first layer formed on the wafer 200 in the raw material supply step can be oxidized. Thus, a second layer formed by oxidizing the first layer is formed on the wafer 200. The second layer is a layer containing the first element, oxygen, carbon, and halogen as the second element.

[0100] In this step, by supplying a catalyst together with a reactant, the above reaction can be carried out in a non-plasma atmosphere and under relatively low temperature conditions as described later. Thus, when the above reaction is carried out, at least a portion of the above chemical bonds (the above chemical bonds in the raw material) contained in the first layer can be maintained without being cut, and at least a portion of the above partial structure (the above partial structure in the molecules of the raw material) contained in the first layer can be maintained without being destroyed. As a result, the second layer becomes a layer containing at least a portion of the above chemical bonds in the raw material and at least a portion of the above partial structure in the molecules of the raw material.

[0101] It should be noted that in this step, when the above reaction is carried out, since at least a part of the above chemical bonds (the above chemical bonds in the raw material) contained in the first layer is not cut but maintained, and at least a part of the above partial structure (the above partial structure in the molecule of the raw material) contained in the first layer is not destroyed but maintained, it is possible to suppress the introduction of the chemical bonds of carbon and hydrogen into the second layer. The second layer becomes a layer with a low content of chemical bonds of carbon and hydrogen, and becomes a layer without chemical bonds of carbon and hydrogen, similarly to the first layer, by the treatment conditions in this step and the oxidant used in this step.

[0102] As the treatment conditions when supplying the reactant and the catalyst in the reactant supply step, the following can be exemplified:

[0103] Treatment temperature: room temperature (25°C) to 200°C, preferably room temperature to 150°C,

[0104] Processing pressure: 133~1333Pa,

[0105] Reactant supply flow rate: 0.001~2slm,

[0106] Catalyst supply flow rate: 0.001~2slm,

[0107] Inert gas supply flow rate (per gas supply pipe): 0~20slm,

[0108] Each gas supply time: 1 to 120 seconds, preferably 1 to 60 seconds.

[0109] After the first layer formed on the wafer 200 is oxidized and changed (converted) to the second layer, the valves 243b and 243c are closed to stop the supply of the reactant and the catalyst into the processing chamber 201. Then, the gaseous substances and the like remaining in the processing chamber 201 are removed (purged) from the processing chamber 201 by the same processing process and processing conditions as those in the purge in the raw material supply step. The processing temperature during the purge in this step is preferably set to the same temperature as the processing temperature during the supply of the reactant and the catalyst.

[0110] As a reactant, that is, an oxidant, for example, a gas containing oxygen (O) and hydrogen (H) (a substance containing O and H) can be used. As a gas containing O and H, for example, water vapor (H2O gas), hydrogen peroxide (H2O2) gas, hydrogen (H2) gas + oxygen (O2) gas, H2 gas + ozone (O3) gas, etc. can be used. That is, as a gas containing O and H, a gas containing O + a gas containing H can also be used. In this case, as a gas containing H, that is, a reducing gas, deuterium (D2) gas can also be used instead of H2 gas. As a reactant, one or more of these can be used.

[0111] It should be noted that the combined description of two gases such as "H2 gas + O2 gas" in this specification refers to a mixed gas of H2 gas and O2 gas. When supplying a mixed gas, the two gases may be mixed (pre-mixed) in a supply pipe and then supplied to the processing chamber 201, or the two gases may be supplied to the processing chamber 201 separately through different supply pipes and mixed (post-mixed) in the processing chamber 201.

[0112] In addition, as a reactant, that is, an oxidant, in addition to a gas containing O and H, a gas containing O (a substance containing O) can also be used. As a gas containing O, for example, O2 gas, O3 gas, nitrous oxide (N2O) gas, nitric oxide (NO) gas, nitrogen dioxide (NO2) gas, carbon monoxide (CO) gas, carbon dioxide (CO2) gas, etc. can be used. As a reactant, one or more of these can be used.

[0113] As the catalyst, for example, the same catalysts as the various catalysts exemplified in the above-mentioned raw material supplying step can be used.

[0114] [Number of times the regulations are implemented]

[0115] By performing the above-mentioned raw material supply step and reactant supply step non-simultaneously, i.e., asynchronously and alternately for a predetermined number of times (n times, n is an integer greater than 1), a film containing the first element, the second element, carbon and halogen can be formed on the wafer 200 as a film.

[0116] The film contains at least a portion of the chemical bonds in the raw material. When the raw material contains chemical bonds between the first element and carbon and chemical bonds between halogen and carbon, the film formed on the wafer 200 contains chemical bonds between the first element and carbon and chemical bonds between halogen and carbon.

[0117] In addition, the film becomes a film containing at least a part of the partial structure of the raw material molecule. In the case where the raw material molecule contains a partial structure in which at least two of the four bonds of the carbon atoms are respectively bonded to the atoms of the halogen and the remaining bonds are respectively bonded to the atoms of the first element, the film formed on the wafer 200 becomes a film containing the partial structure, that is, Figure 5 (a) Figure 5 (b) Partial structure of the membrane shown.

[0118] In addition, as described above, the first layer becomes a layer that does not contain chemical bonds between carbon and hydrogen. In addition, the second layer becomes a layer that contains less chemical bonds between carbon and hydrogen, or, like the first layer, becomes a layer that does not contain chemical bonds between carbon and hydrogen. According to these conditions, the film formed on the wafer 200 becomes a film that contains less chemical bonds between carbon and hydrogen or a film that does not contain chemical bonds between carbon and hydrogen.

[0119] When Cl3Si-CF2-SiCl3 containing Si as the first element is used as the raw material, the above-mentioned oxidant containing O as the second element is used as the reactant, and the above-mentioned catalyst is used, a film containing Si, O, C and F as a halogen, that is, a silicon oxycarbide film (SiOC film) containing F can be formed as a film on the wafer 200. The film becomes a film containing chemical bonds (Si-C-Si bonds, FC bonds) in the raw material and a partial structure of the molecules of the raw material (Si-CF2-Si). The film becomes a film with a low content of CH bonds or a film without CH bonds.

[0120] In addition, when Cl3Si-CCl2-SiCl3 containing Si as the first element is used as the raw material, the above-mentioned oxidant containing O as the second element is used as the reactant, and the above-mentioned catalyst is used, a film containing Si, O, C and Cl as a halogen, that is, a SiOC film containing Cl can be formed as a film on the wafer 200. The film becomes a film containing chemical bonds (Si-C-Si bonds, Cl-C bonds) in the raw material and a partial structure of the molecules of the raw material (Si-CCl2-Si). The film becomes a film with a low content of CH bonds or a film without CH bonds.

[0121] In addition, when Cl3Si-CF3 containing Si as the first element is used as the raw material, the above-mentioned oxidant containing O as the second element is used as the reactant, and the above-mentioned catalyst is used, a film containing Si, O, C and F as a halogen, that is, a SiOC film containing F can be formed as a film on the wafer 200. The film becomes a film containing chemical bonds (Si-C bonds, FC bonds) in the raw material and a partial structure of the molecules of the raw material (Si-CF3). The film becomes a film with a low content of CH bonds or a film without CH bonds.

[0122] In addition, when Cl3Si-CCl3 containing Si as the first element is used as the raw material, the above-mentioned oxidant containing O as the second element is used as the reactant, and the above-mentioned catalyst is used, a film containing Si, O, C and Cl as a halogen, that is, a SiOC film containing Cl can be formed as a film on the wafer 200. The film becomes a film containing chemical bonds (Si-C bonds, Cl-C bonds) in the raw material and a partial structure of the molecules of the raw material (Si-CCl3). The film becomes a film with a low content of CH bonds or a film without CH bonds.

[0123] The above cycle is preferably repeated a plurality of times. That is, the above cycle is preferably repeated a plurality of times until the thickness of the second layer formed in each cycle is thinner than the desired film thickness and the film thickness formed by laminating the second layer reaches the desired film thickness.

[0124] (Heat treatment step)

[0125] After the film forming step, the wafer 200 after the film is formed is heat treated. At this time, the output of the heater 207 is adjusted so that the temperature in the processing chamber 201, that is, the temperature of the wafer 200 after the film is formed, is set to be higher than the temperature of the wafer 200 in the film forming step.

[0126] By heat treating (annealing) the wafer 200, impurities contained in the film formed on the wafer 200 in the film forming step can be removed or defects can be repaired, and the film can be hardened. By hardening the film, the processing resistance of the film, that is, the etching resistance, can be improved. It should be noted that in the film formed on the wafer 200, when the removal of impurities, the repair of defects, or the hardening of the film is not required, the annealing treatment, that is, the heat treatment step, can also be omitted.

[0127] It should be noted that this step can be performed while supplying an inert gas or a reactive substance such as an oxidant (oxidizing gas) into the processing chamber 201. In this case, the inert gas or reactive substance such as an oxidant (oxidizing gas) is also called an auxiliary substance.

[0128] The treatment conditions for heat treatment in the heat treatment step include:

[0129] Processing temperature: 200-1000°C, preferably 400-700°C,

[0130] Processing pressure: 1~120000Pa,

[0131] Processing time: 1 to 18,000 seconds,

[0132] Auxiliary material supply flow rate: 0~50slm.

[0133] (Post-purge and atmospheric pressure recovery)

[0134] After the heat treatment step is completed, an inert gas as a purge gas is supplied from the nozzles 249a to 249c into the processing chamber 201, and the purge gas is exhausted from the exhaust port 231a. Thus, the processing chamber 201 is purged, and the gas, reaction by-products, etc. remaining in the processing chamber 201 are removed from the processing chamber 201 (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 normal pressure (atmospheric pressure restoration).

[0135] (Cassette unloading and wafer release)

[0136] Then, the sealing cover 219 is lowered by the wafer box elevator 115 to open the lower end of the manifold 209. Then, the processed wafer 200 is carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the wafer box 217 (wafer box unloading). After the wafer box is unloaded, the baffle 219s is moved to seal the lower end opening of the manifold 209 through the O-ring 220c and the baffle 219s (baffle closing). After the processed wafer 200 is carried out to the outside of the reaction tube 203, it is taken out by the wafer box 217 (wafer release).

[0137] The film forming step and the heat treatment step are preferably performed in the same processing chamber (in-situ). Thus, the wafer 200 can be kept clean without being exposed to the atmosphere, that is, the film forming step and the heat treatment step can be performed. By performing these steps in the same processing chamber, the film quality of the film formed on the wafer 200 can be prevented from being reduced.

[0138] (3) Effects of this method

[0139] According to this aspect, one or more of the following effects can be obtained.

[0140] (a) By performing a cycle including the following steps for a predetermined number of times, the film quality of a film formed on the wafer 200, i.e., a film containing a first element, a second element, carbon and a halogen, can be improved. The above steps are a raw material supply step of supplying a raw material containing the first element, carbon and a halogen and not containing a chemical bond between carbon and hydrogen, and a reactant supply step of supplying a reactant containing a second element different from the first element.

[0141] That is, according to this method, by using a raw material containing a first element, carbon and a halogen and not containing a chemical bond between carbon and hydrogen, the content of the chemical bond between the first element and carbon in the film formed on the wafer 200 can be increased without excessively, thereby reducing the content of the chemical bond between carbon and hydrogen in the film. As a result, the amount of the chemical bond between the first element and carbon in the film can be appropriately maintained and the carbon can be inhibited from escaping from the oxidized film. As a result, the increase in the relative dielectric constant (k value) caused by the high density of the film formed on the wafer 200 can be suppressed, and the ashing resistance (oxidation resistance, plasma oxidation resistance) that is one of the processing resistances of the film can be improved. That is, the low dielectric constant (Low-k) of the film, which is in a trade-off relationship, and the improvement of the ashing resistance can be taken into account. In addition, the etching resistance (wet etching resistance) that is one of the processing resistances of the film before and after ashing can also be improved.

[0142] It should be noted that, as disclosed in Patent Document 1, a film containing a first element, a second element, carbon, and fluorine can be formed by using a raw material containing a chemical bond between a first element and carbon and a chemical bond between carbon and hydrogen, a reactant containing a second element, and a catalyst to form a film, and using a fluorine-based gas to modify the film. However, in this method, since the raw material contains a chemical bond between carbon and hydrogen, it is difficult to obtain the above-mentioned effect. In addition, there is also a case where etching of the film occurs depending on the processing conditions.

[0143] (b) By supplying a raw material containing a chemical bond between the first element and carbon and a chemical bond between a halogen and carbon in the raw material supply step, the film formed on the wafer 200 can contain these chemical bonds. As a result, the increase in the k value of the film can be suppressed and the ashing resistance of the film can be further improved. In addition, the etching resistance of the film before and after ashing can be further improved.

[0144] (c) By having the molecules of the raw material supplied in the raw material supplying step contain the above-mentioned partial structure in which at least two of the four bonds of the carbon atom are respectively bonded to the atoms of the halogen and the remaining bonds are respectively bonded to the atoms of the first element, the film formed on the wafer 200 can contain the partial structure. Thus, the increase in the k value of the film can be suppressed and the ashing resistance of the film can be further improved. In addition, the etching resistance of the film before and after ashing can be further improved.

[0145] For example, the molecules of the raw material supplied in the raw material supply step include Figure 5 The partial structure of the type shown in (a), that is, a partial structure in which two of the four bonds of the carbon atom are respectively bonded to the atoms of the halogen and the remaining two bonds are respectively bonded to the atoms of the first element, can cause the film formed on the wafer 200 to contain the partial structure. For example, in the case where Cl3Si-CF2-SiCl3 is supplied as a raw material, a film containing Si as the first element, F as the halogen, and Si-CF2-Si as the above-mentioned partial structure can be formed on the wafer 200. In addition, for example, in the case where Cl3Si-CCl2-SiCl3 is supplied as a raw material, a film containing Si as the first element, Cl as the halogen, and Si-CCl2-Si as the above-mentioned partial structure can be formed on the wafer 200. In these cases, the increase in the k value of the film can be sufficiently suppressed and the ashing resistance of the film can be sufficiently improved. In addition, the etching resistance of the film before and after ashing can be sufficiently improved.

[0146] In addition, for example, by the molecules of the raw material supplied in the raw material supply step comprising Figure 5The partial structure of the type shown in (b), that is, a partial structure in which three of the four bonds of the carbon atom are respectively bonded to halogen atoms and the remaining one is bonded to an atom of the first element, can cause the film formed on the wafer 200 to contain the partial structure. For example, in the case where Cl3Si-CF3 is supplied as a raw material, a film containing Si as the first element, F as a halogen, and Si-CF3 as the above-mentioned partial structure can be formed on the wafer 200. In addition, for example, in the case where Cl3Si-CCl3 is supplied as a raw material, a film containing Si as the first element, Cl as a halogen, and Si-CCl3 as the above-mentioned partial structure can be formed on the wafer 200. In these cases, the increase in the k value of the film can be sufficiently suppressed and the ashing resistance of the film can be sufficiently improved. In addition, the etching resistance of the film before and after ashing can be sufficiently improved.

[0147] (d) The above effect can be more significantly achieved by further supplying a catalyst to the wafer 200 in at least one of the raw material supplying step and the reactant supplying step. The reason is that by supplying a catalyst, when the raw material or the reactant is present alone in the processing chamber 201, these are thermally decomposed (gas phase decomposed), that is, under low temperature processing conditions such as no self-decomposition, the above film forming reaction can be carried out.

[0148] That is, in the raw material supplying step, by supplying a raw material containing a chemical bond between the first element and carbon and a chemical bond between a halogen and carbon to the wafer 200 and further supplying a catalyst, the first layer can be formed under the condition that the chemical bonds between the first element and carbon and the chemical bonds between the halogen and carbon in the raw material are not cut but maintained. As a result, the first layer can contain more chemical bonds between the first element and carbon and chemical bonds between the halogen and carbon.

[0149] In addition, by supplying a reactant containing a second element different from the first element to the wafer 200 and further supplying a catalyst in the reactant supplying step, the second layer can be formed under the condition that the chemical bonds between the first element and carbon and the chemical bonds between the halogen and carbon in the raw material (contained in the first layer) are not cut and are maintained. As a result, the second layer can contain more chemical bonds between the first element and carbon and the chemical bonds between the halogen and carbon.

[0150] As described above, when a raw material containing chemical bonds between a first element and carbon and chemical bonds between a halogen and carbon is supplied to the wafer 200 in the raw material supplying step, and a catalyst is further supplied to the wafer 200 in at least any one of the raw material supplying step and the reactant supplying step, the film formed on the wafer 200 can contain more chemical bonds between the first element and carbon and chemical bonds between a halogen and carbon.

[0151] Furthermore, in at least one of the raw material supplying step and the reactant supplying step, when a catalyst is further supplied to the wafer 200, the chemical bonds contained in the first layer and the second layer are not cut but maintained, so that the chemical bonds of carbon and hydrogen can be suppressed from being introduced into the first layer and the second layer. As a result, the film formed on the wafer 200 can be made into a film having a lower content of chemical bonds of carbon and hydrogen or a film containing no chemical bonds of carbon and hydrogen.

[0152] This can suppress an increase in the k value of the film and further improve the ashing resistance of the film. In addition, the etching resistance of the film before and after ashing can be further improved.

[0153] In addition, in the raw material supplying step, by supplying a raw material including the above-mentioned partial structure in which at least two of the four bonds of carbon atoms are respectively bonded to halogen atoms and the remaining bonds are respectively bonded to atoms of the first element to the wafer 200 and further supplying a catalyst, the first layer can be formed while maintaining the above-mentioned partial structure without destroying it. As a result, the first layer can contain more of the above-mentioned partial structure.

[0154] In addition, by supplying a reactant containing a second element different from the first element and further supplying a catalyst to the wafer 200 in the reactant supplying step, the second layer can be formed without destroying the above-mentioned partial structure contained in the first layer and maintaining it. As a result, the second layer can contain more of the above-mentioned partial structure.

[0155] Thus, in the raw material supplying step, a raw material including the above-mentioned partial structure is supplied to the wafer 200, and in at least any one of the raw material supplying step and the reactant supplying step, a catalyst is further supplied to the wafer 200, so that the film formed on the wafer 200 can contain more of the above-mentioned partial structure.

[0156] Furthermore, in at least one of the raw material supplying step and the reactant supplying step, when a catalyst is further supplied to the wafer 200, the partial structure contained in the first layer and the second layer is not destroyed but maintained, so that the chemical bonds of carbon and hydrogen can be suppressed from being introduced into the first layer and the second layer. As a result, the film formed on the wafer 200 can be made into a film having a lower content of the chemical bonds of carbon and hydrogen or a film containing no chemical bonds of carbon and hydrogen.

[0157] This can suppress an increase in the k value of the film and further improve the ashing resistance of the film. In addition, the etching resistance of the film before and after ashing can be further improved.

[0158] (e) When a predetermined substance (gaseous substance, liquid substance) is arbitrarily selected from the above-mentioned various raw materials, various reactants, various catalysts, and various inert gases for use, the above-mentioned effect can also be obtained in the same manner. It should be noted that, when the halogen contained in the raw material is any one of Cl, F, Br, and I, the above-mentioned effect can also be obtained. In addition, when the halogen contained in the raw material is Cl or F, the above-mentioned effect can be obviously obtained.

[0159] <Other aspects of the present invention>

[0160] Although the embodiments of the present invention have been specifically described above, the present invention is not limited to the above embodiments, and various modifications can be made without departing from the gist of the present invention.

[0161] For example, the present invention can also be applied to the case where a film containing semiconductor elements such as silicon (Si) and germanium (Ge), and metal elements such as titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), aluminum (Al), molybdenum (Mo), tungsten (W), and ruthenium (Ru) as the first element is formed on a substrate. The processing process and processing conditions when supplying the film-forming agent can be the same as those in the steps of the above-mentioned method. In these cases, the same effects as those of the above-mentioned method can also be obtained.

[0162] In addition, for example, the present invention can also be applied to the case where a film containing an element such as oxygen (O), carbon (C), nitrogen (N), boron (B) as a second element is formed on a substrate. For example, the present invention can also be applied to the case where a silicon oxide carbide film (SiOC film), a silicon oxide carbon nitride film (SiOCN film), a silicon carbonitride film (SiCN film), a silicon boron carbide film (SiBC film), a silicon boron carbonitride film (SiBCN film), etc. are formed on a substrate through the above-mentioned process using the above-mentioned oxygen-containing gas, carbon-containing gases such as ethylene (C2H4) gas, acetylene (C2H2) gas, propylene (C3H6) gas, nitrogen-containing gases such as ammonia (NH3) gas, diimide (N2H2) gas, nitrogen- and carbon-containing gases such as triethylamine ((C2H5)3N) gas, trimethylamine ((CH3)3N) gas, and boron-containing gases such as diborane (B2H6) gas and trichloroborane (BCl3) gas as reactants. The process and conditions for supplying the film-forming agent may be the same as those in the steps of the above-mentioned embodiment. In these cases, the same effects as those of the above-mentioned embodiment can be obtained.

[0163] The recipe for each treatment is preferably prepared individually in accordance with the treatment content, and recorded and stored in the storage device 121c via a telecommunication line and an external storage device 123. Moreover, when each treatment is started, the CPU 121a selects a suitable recipe from the plurality of recipes recorded and stored in the storage device 121c in accordance with the treatment content. Thus, a film of various film types, composition ratios, film qualities, and film thicknesses can be formed with good reproducibility using one substrate processing device. In addition, the burden on the operator can be reduced, operational errors can be avoided, and each treatment can be started quickly.

[0164] The above-mentioned recipe is not limited to the case of newly preparing, for example, it can also be prepared by changing an existing recipe already installed in the substrate processing device. When changing the recipe, the changed recipe can also be installed in the substrate processing device via a telecommunication line or a recording medium recording the recipe. In addition, the input / output device 122 of the existing substrate processing device can also be operated to directly change the existing recipe already installed in the substrate processing device.

[0165] In the above-mentioned method, an example of forming a film using a batch-type substrate processing device that processes a plurality of substrates at a time is described. The present invention is not limited to the above-mentioned method, and for example, it can also be preferably applied to a case where a film is formed using a monolithic substrate processing device that processes one or more substrates at a time. In addition, in the above-mentioned method, an example of forming a film using a substrate processing device having a hot-wall type processing furnace is described. The present invention is not limited to the above-mentioned method, and it can also be preferably applied to a case where a film is formed using a substrate processing device having a cold-wall type processing furnace.

[0166] When these substrate processing apparatuses are used, each process can be performed in the same process procedure and process conditions as those of the above-mentioned embodiment and modified example, and the same effects as those of the above-mentioned embodiment and modified example can be obtained.

[0167] The above-mentioned aspects and modifications may be used in combination as appropriate. The processing procedure and processing conditions at this time may be, for example, the same as those of the above-mentioned aspects and modifications.

[0168] Explanation of symbols

[0169] 200: Wafer (substrate).

Claims

1. A substrate processing method, comprising the step of forming a film containing a first element, a second element, carbon and a halogen on a substrate by performing a cycle including steps (a) and (b) a predetermined number of times; The step (a) is a step of supplying a raw material containing the first element, carbon and halogen and not containing a chemical bond between carbon and hydrogen to the substrate; The step (b) is a step of supplying a reactant containing the second element different from the first element to the substrate.

2. The substrate processing method according to claim 1, wherein: The raw material contains a chemical bond between the first element and carbon and a chemical bond between the halogen and carbon.

3. The substrate processing method according to claim 2, wherein: The molecule of the raw material includes a partial structure in which at least two of the four bonds of the carbon atom are respectively bonded to the halogen atom and the remaining bonds are respectively bonded to the atom of the first element.

4. The substrate processing method according to claim 2, wherein: The molecule of the raw material includes a partial structure in which two of the four bonds of the carbon atom are respectively bonded to the halogen atom and the remaining two bonds are respectively bonded to the atom of the first element.

5. The substrate processing method according to claim 4, wherein: The first element includes silicon (Si), the halogen includes fluorine (F), and the partial structure includes Si-CF2-Si.

6. The substrate processing method according to claim 4, wherein: The first element includes silicon (Si), the halogen includes chlorine (Cl), and the partial structure includes Si-CCl2-Si.

7. The substrate processing method according to claim 2, wherein: The molecule of the raw material includes a partial structure in which three of the four bonds of the carbon atom are respectively bonded to the halogen atom and the remaining one is bonded to the atom of the first element.

8. The substrate processing method according to claim 7, wherein: The first element includes silicon (Si), the halogen includes fluorine (F), and the partial structure includes Si-CF3.

9. The substrate processing method according to claim 7, wherein: The first element includes silicon (Si), the halogen includes chlorine (Cl), and the partial structure includes Si-CCl3.

10. The substrate processing method according to any one of claims 1 to 9, wherein: The second element includes oxygen.

11. The substrate processing method according to any one of claims 1 to 9, wherein: The reactant is an oxidizing agent.

12. The substrate processing method according to any one of claims 1 to 9, wherein: In at least any one of the steps (a) and (b), a catalyst is further supplied to the substrate.

13. The substrate processing method according to claim 2, wherein: (a) and (b) are performed under the condition that the chemical bond between the first element and carbon and the chemical bond between the halogen and carbon in the raw material are not cut but maintained.

14. The substrate processing method according to claim 13, wherein: The film contains a chemical bond between the first element and carbon and a chemical bond between the halogen and carbon.

15. The substrate processing method according to any one of claims 3, 4 and 7, wherein: (a) and (b) are performed under the condition that the partial structure is not destroyed but maintained.

16. The substrate processing method according to claim 15, wherein: The film contains the partial structure.

17. The substrate processing method according to any one of claims 1 to 9, wherein: The film contains no chemical bonds of carbon and hydrogen.

18. A method for manufacturing a semiconductor device, comprising the step of forming a film containing a first element, a second element, carbon and a halogen on a substrate by performing a cycle including steps (a) and (b) a predetermined number of times; The step (a) is a step of supplying a raw material containing the first element, carbon and halogen and not containing a chemical bond between carbon and hydrogen to the substrate; The step (b) is a step of supplying a reactant containing the second element different from the first element to the substrate.

19. A substrate processing device, comprising: a processing chamber for processing substrates, a raw material supply system for supplying a raw material containing a first element, carbon, and halogen and not containing a chemical bond between carbon and hydrogen to the substrate in the processing chamber; a reactant supply system for supplying a reactant containing a second element different from the first element to the substrate in the processing chamber, and Control Department; The control unit is configured to control the raw material supply system and the reactant supply system so as to form a film containing the first element, the second element, carbon and halogen on the substrate in the processing chamber by performing a cycle including (a) supplying the raw material to the substrate and (b) supplying the reactant to the substrate for a predetermined number of times.

20. A program that uses a computer to cause a substrate processing device to execute the following steps: In the step, a film containing the first element, the second element, carbon and the halogen is formed on the substrate by performing a cycle including the step (a) and the step (b) a predetermined number of times; The step (a) is a step of supplying a raw material containing the first element, carbon and halogen and not containing a chemical bond between carbon and hydrogen to the substrate; The step (b) is a step of supplying a reactant containing the second element different from the first element to the substrate.

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