WO2022180825A1 - 半導体装置の製造方法、基板処理装置、およびプログラム - Google Patents
半導体装置の製造方法、基板処理装置、およびプログラム Download PDFInfo
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- WO2022180825A1 WO2022180825A1 PCT/JP2021/007506 JP2021007506W WO2022180825A1 WO 2022180825 A1 WO2022180825 A1 WO 2022180825A1 JP 2021007506 W JP2021007506 W JP 2021007506W WO 2022180825 A1 WO2022180825 A1 WO 2022180825A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/308—Oxynitrides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
- H01L21/0214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being a silicon oxynitride, e.g. SiON or SiON:H
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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- C23C16/45523—Pulsed gas flow or change of composition over time
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- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/45546—Atomic layer deposition [ALD] characterized by the apparatus specially adapted for a substrate stack in the ALD reactor
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- H01L21/02222—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen the compound being a silazane
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- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
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- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
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- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
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Definitions
- the present disclosure relates to a semiconductor device manufacturing method, a substrate processing apparatus, and a program.
- a substrate processing step is performed in which a material, an oxidizing agent, and a nitriding agent are supplied to a substrate to form a film containing a predetermined element, oxygen, and nitrogen on the substrate (for example, see Patent Document 1).
- An object of the present disclosure is to improve the composition ratio controllability of a film containing a predetermined element, oxygen, and nitrogen formed on a substrate.
- supplying a first raw material containing a predetermined element to the substrate (b) supplying to the substrate a second source material having a molecular structure different from that of the first source material and containing the predetermined element and oxygen; (c) supplying an oxidizing agent to the substrate; (d) supplying a nitriding agent to the substrate; is performed a predetermined number of times to form a film containing the predetermined element, oxygen and nitrogen on the substrate.
- FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one aspect of the present disclosure, and is a longitudinal sectional view showing a processing furnace 202 portion.
- FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one aspect of the present disclosure, and is a cross-sectional view showing the processing furnace 202 portion taken along line AA of FIG.
- FIG. 3 is a schematic configuration diagram of the controller 121 of the substrate processing apparatus preferably used in one aspect of the present disclosure, and is a block diagram showing the control system of the controller 121.
- FIG. 4 is a flow diagram illustrating a gas supply sequence in one aspect of the present disclosure.
- FIG. 4 is a diagram schematically showing the surface state of a substrate before starting film formation.
- FIG. 10 is a diagram schematically showing the surface state of the substrate when step B is carried out;
- FIG. 10 is a diagram schematically showing the surface state of the substrate when step A is performed after step B is completed;
- FIG. 10 is a diagram schematically showing the surface state of the substrate when step C is performed after steps B and A are completed;
- FIG. 10 is a diagram schematically showing the surface state of the substrate when step D is performed after steps B, A, and C are completed;
- 4A and 4B are diagrams illustrating various measurement results of a film formed on a substrate;
- FIG. 10 is a diagram schematically showing the surface state of the substrate when step B is carried out;
- FIG. 10 is a diagram schematically showing the surface state of the substrate when step A is performed after step B is completed;
- FIG. 10 is a diagram schematically showing the surface state of the substrate when step C is performed after steps B and A are completed;
- FIGS. 1-4 and 5A-5E One aspect of the present disclosure will now be described primarily with reference to FIGS. 1-4 and 5A-5E.
- the drawings used in the following description are all schematic, and the dimensional relationship of each element on the drawings, the ratio of each element, etc. do not necessarily match the actual ones. Moreover, the dimensional relationship of each element, the ratio of each element, etc. do not necessarily match between a plurality of drawings.
- the processing furnace 202 has a heater 207 as a temperature controller (heating unit).
- the heater 207 has a cylindrical shape and is installed vertically by being supported by a holding plate.
- the heater 207 also functions as an activation mechanism (excitation section) that thermally activates (excites) the gas.
- a reaction tube 203 is arranged concentrically with the heater 207 inside the heater 207 .
- the reaction tube 203 is made of a heat-resistant material such as quartz (SiO 2 ) or silicon carbide (SiC), and has a cylindrical shape with a closed upper end and an open lower end.
- a manifold 209 is arranged concentrically with the reaction tube 203 below the reaction tube 203 .
- the manifold 209 is made of a metal material such as stainless steel (SUS), and is formed in a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 engages the lower end of the reaction tube 203 and is configured to support the reaction tube 203 .
- An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a sealing member.
- Reactor tube 203 is mounted vertically like heater 207 .
- a processing vessel (reaction vessel) is mainly configured by the reaction tube 203 and the manifold 209 .
- a processing chamber 201 is formed in the cylindrical hollow portion of the processing container. The processing chamber 201 is configured to accommodate a wafer 200 as a substrate. A wafer 200 is processed in the processing chamber 201 .
- nozzles 249a to 249c as first to third supply units are provided so as to pass through the side wall of the manifold 209, respectively.
- the nozzles 249a to 249c are also called first to third nozzles, respectively.
- the nozzles 249a-249c are made of a heat-resistant material such as quartz or SiC.
- Gas supply pipes 232a to 232c are connected to the nozzles 249a to 249c, respectively.
- the nozzles 249a to 249c are different nozzles, and each of the nozzles 249b and 249c is provided adjacent to the nozzle 249a.
- the gas supply pipes 232a to 232c are provided with mass flow controllers (MFC) 241a to 241c as flow rate controllers (flow rate control units) and valves 243a to 243c as on-off valves in this order from the upstream side of the gas flow. .
- Gas supply pipes 232d and 232e are connected downstream of the valve 243a of the gas supply pipe 232a.
- Gas supply pipes 232f and 232g are connected downstream of the valves 243b and 243c of the gas supply pipes 232b and 232c.
- the gas supply pipes 232e to 232g are provided with MFCs 241e to 241g and valves 243e to 243g, respectively, in this order from the upstream side of the gas flow.
- the gas supply pipes 232a to 232g are made of metal material such as SUS.
- the nozzles 249a to 249c are arranged in an annular space between the inner wall of the reaction tube 203 and the wafer 200 in a plan view, along the inner wall of the reaction tube 203 from the lower part to the upper part. They are provided so as to rise upward in the arrangement direction.
- the nozzles 249a to 249c are provided on the sides of the wafer arrangement area in which the wafers 200 are arranged, in a region horizontally surrounding the wafer arrangement area, along the wafer arrangement area.
- the nozzle 249a is arranged so as to face an exhaust port 231a, which will be described later, in a straight line with the center of the wafer 200 loaded into the processing chamber 201 interposed therebetween.
- the nozzles 249b and 249c are arranged along the inner wall of the reaction tube 203 (peripheral portion of the wafer 200) to sandwich a straight line L passing through the center of the nozzle 249a and the exhaust port 231a from both sides.
- the straight line L is also a straight line passing through the nozzle 249 a and the center of the wafer 200 . That is, it can be said that the nozzle 249c is provided on the opposite side of the straight line L from the nozzle 249b.
- the nozzles 249b 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.
- Each of the gas supply holes 250a to 250c is open to face the exhaust port 231a in a plan view, and is capable of supplying gas toward the wafer 200. As shown in FIG. A plurality of gas supply holes 250 a to 250 c are provided from the bottom to the top of the reaction tube 203 .
- a first raw material (first raw material gas) containing a predetermined element is supplied from the gas supply pipe 232a into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.
- An oxidant (oxidizing gas) is supplied from the gas supply pipe 232b into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.
- a nitriding agent (nitriding gas) is supplied from the gas supply pipe 232c into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.
- a second source material (second source gas) having a molecular structure different from that of the above-described first source material and containing a predetermined element and oxygen (O) is supplied to the MFC 241d, the valve 243d, the gas supply pipe 232a, and the nozzle. 249a into the processing chamber 201.
- the inert gas is supplied to the processing chamber through the MFCs 241e, 241f, 241g, the valves 243e, 243f, 243g, the gas supply pipes 232a, 232b, 232c, and the nozzles 249a, 249b, 249c.
- Inert gases act as purge gas, carrier gas, diluent gas, and the like.
- a first raw material supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a.
- An oxidant supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b.
- a nitriding agent supply system is mainly composed of the gas supply pipe 232c, the MFC 241c, and the valve 243c.
- a second raw material supply system is mainly composed of the gas supply pipe 232d, the MFC 241d, and the valve 243d.
- An inert gas supply system is mainly composed of gas supply pipes 232e to 232g, MFCs 241e to 241g, and valves 243e to 243g.
- At least one of the first raw material gas, the second raw material gas, the oxidizing gas, and the nitriding gas is also referred to as a film-forming gas. is also referred to as a deposition gas supply system.
- any or all of the gas supply systems described above may be configured as an integrated gas supply system 248 in which valves 243a to 243g, MFCs 241a to 241g, etc. are integrated.
- the integrated gas supply system 248 is connected to each of the gas supply pipes 232a to 232g, and supplies various gases to the gas supply pipes 232a to 232g, that is, the opening and closing operations of the valves 243a to 243g and the MFCs 241a to 241g. is configured to be controlled by a controller 121, which will be described later.
- the integrated gas supply system 248 is configured as an integrated unit or a divided integrated unit, and can be attached/detached to/from the gas supply pipes 232a to 232g or the like in units of the integrated unit. H.248 maintenance, replacement, expansion, etc. can be performed for each integrated unit.
- An exhaust port 231 a for exhausting the atmosphere in the processing chamber 201 is provided below the side wall of the reaction tube 203 . As shown in FIG. 2, the exhaust port 231a is provided at a position facing the nozzles 249a to 249c (gas supply holes 250a to 250c) across the wafer 200 in plan view. The exhaust port 231a may be provided along the upper portion of the side wall of the reaction tube 203, that is, along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a.
- the exhaust pipe 231 is made of, for example, a metal material such as SUS.
- the exhaust pipe 231 is supplied with a pressure sensor 245 as a pressure detector (pressure detector) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure regulator).
- a vacuum pump 246 as an evacuation device is connected.
- An exhaust system is mainly composed of the exhaust pipe 231 , the APC valve 244 and the pressure sensor 245 .
- a vacuum pump 246 may be considered to be included in the exhaust system.
- a seal cap 219 is provided below the manifold 209 as a furnace mouth cover capable of airtightly closing the lower end opening of the manifold 209 .
- the seal cap 219 is made of, for example, a metal material such as SUS, and is shaped like a disc.
- An O-ring 220 b is provided on the upper surface of the seal cap 219 as a sealing member that contacts the lower end of the manifold 209 .
- a rotating mechanism 267 for rotating the boat 217 which will be described later, is installed below the seal cap 219.
- a rotating shaft 255 of the rotating mechanism 267 is made of a metal material such as SUS, and is connected to the boat 217 through the seal cap 219 .
- the rotating mechanism 267 is configured to rotate the wafers 200 by rotating the boat 217 .
- the seal cap 219 is vertically moved up and down by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203 .
- the boat elevator 115 is configured as a transport device (transport mechanism) for loading and unloading (transporting) the wafer 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219 .
- a shutter 219s is provided as a furnace port cover that can hermetically close the lower end opening of the manifold 209 in a state where the seal cap 219 is lowered and the boat 217 is carried out from the processing chamber 201.
- the shutter 219s is made of a metal material such as SUS, and is shaped like a disc.
- An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that contacts the lower end of the manifold 209. As shown in FIG.
- the opening/closing operation (elevating operation, rotating operation, etc.) of the shutter 219s is controlled by the shutter opening/closing mechanism 115s.
- the boat 217 as a substrate support supports a plurality of wafers 200, for example, 25 to 200 wafers 200, in a horizontal posture, aligned vertically with their centers aligned with each other, and supported in multiple stages. It is configured to be spaced and arranged.
- the boat 217 is made of a heat-resistant material such as quartz or SiC.
- a plurality of heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported.
- a temperature sensor 263 as a temperature detector is installed in the reaction tube 203 .
- the temperature inside the processing chamber 201 has a desired temperature distribution.
- a temperature sensor 263 is provided along the inner wall of the reaction tube 203 .
- the controller 121 which is a control unit (control means), is configured as a computer comprising a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I/O port 121d. It is 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 configured as, for example, a touch panel or the like is connected to the controller 121 .
- the storage device 121c is composed of, for example, flash memory, HDD (Hard Disk Drive), SSD (Solid State Drive), and the like.
- a control program for controlling the operation of the substrate processing apparatus, a process recipe describing procedures and conditions for substrate processing, which will be described later, and the like are stored in a readable manner.
- the process recipe functions as a program in which the controller 121 executes each procedure in substrate processing, which will be described later, and is combined so as to obtain a predetermined result.
- process recipes, control programs, and the like are collectively referred to simply as programs.
- a process recipe is also simply referred to as a recipe.
- the RAM 121b is configured as a memory area (work area) in which programs and data read by the CPU 121a are temporarily held.
- the I/O port 121d includes the MFCs 241a to 241g, valves 243a to 243g, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotating mechanism 267, boat elevator 115, shutter opening/closing mechanism 115s, and the like. It is connected to the.
- the CPU 121a is configured to be able to read and execute a control program from the storage device 121c, and read recipes from the storage device 121c in response to input of operation commands from the input/output device 122, and the like.
- the CPU 121a adjusts the flow rate of various gases by the MFCs 241a to 241g, the opening and closing operations of the valves 243a to 243g, the opening and closing operations of the APC valve 244, and the pressure adjustment by the APC valve 244 based on the pressure sensor 245 so as to follow the content of the read recipe.
- shutter opening/closing mechanism 115s is configured to be able to control the opening/closing operation of the shutter 219s and the like.
- the controller 121 can be configured by installing the above-described program stored in the external storage device 123 in the computer.
- the external storage device 123 includes, for example, a magnetic disk such as an HDD, an optical disk such as a CD, a magneto-optical disk such as an MO, a semiconductor memory such as a USB memory or an SSD, and the like.
- the storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are also collectively referred to simply as recording media.
- recording medium may include only the storage device 121c alone, may include only the external storage device 123 alone, or may include both of them.
- the program may be provided to the computer using communication means such as the Internet or a dedicated line without using the external storage device 123 .
- steps A and B are followed by steps C and D, in particular if steps A, B, C, D are performed non-simultaneously, more particularly steps B, A, C, D are performed in this order.
- wafer When the term “wafer” is used in this specification, it may mean the wafer itself, or it may mean a laminate of a wafer and a predetermined layer or film formed on its surface.
- wafer surface may mean the surface of the wafer itself or the surface of a predetermined layer formed on the wafer.
- formation of a predetermined layer on a wafer refers to the direct formation of a predetermined layer on the surface of the wafer itself, or the formation of a layer formed on the wafer. It may mean forming a given layer on top.
- substrate in this specification is synonymous with the use of the term "wafer”.
- the shutter 219s is moved by the shutter opening/closing mechanism 115s to open the lower end opening of the manifold 209 (shutter open). Thereafter, as shown in FIG. 1, the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and loaded into the processing chamber 201 (boat load). In this state, the seal cap 219 seals the lower end of the manifold 209 via the O-ring 220b.
- the inside of the processing chamber 201 that is, the space in which the wafer 200 exists is evacuated (reduced pressure) by the vacuum pump 246 so as to have a desired pressure (degree of vacuum).
- 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 (pressure adjustment).
- the wafer 200 in the processing chamber 201 is heated by the heater 207 so as to reach a desired processing temperature.
- the energization state of the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution (temperature adjustment).
- the rotation of the wafer 200 by the rotation mechanism 267 is started. The evacuation of the processing chamber 201 and the heating and rotation of the wafer 200 continue at least until the processing of the wafer 200 is completed.
- the surface of the wafer 200 is terminated (OH-terminated) with hydroxyl groups (--OH).
- OH termination present on the surface of the wafer 200 functions as an adsorption site for molecules and atoms.
- Step B the second raw material is supplied to the wafer 200 inside the processing chamber 201 .
- valve 243d is opened to allow the second raw material to flow into the gas supply pipe 232d.
- the flow rate of the second raw material is adjusted by the MFC 241d, supplied into the processing chamber 201 through the gas supply pipe 232a and the nozzle 249a, and exhausted from the exhaust port 231a.
- the second raw material is supplied to the wafer 200 (second raw material supply).
- the valves 243e to 243g are opened to supply the inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively. In some methods described below, the supply of the inert gas into the processing chamber 201 may be disabled.
- a gas having a molecular structure containing an alkoxy group bonded to silicon (Si) as a predetermined element can be used.
- a gas in which an amino group is bonded to one bond of Si as a predetermined element constituting the central atom X and an alkoxy group is bonded to the remaining three bonds can be used.
- the amino group has a structure obtained by removing hydrogen (H) from any of ammonia (NH 3 ), primary amine, and secondary amine, and among —NH 2 , —NHR, and —NRR′
- R and R' shown in the structural formulas are alkyl groups including methyl, ethyl, propyl and butyl groups.
- R and R' may be not only these linear alkyl groups but also branched alkyl groups such as isopropyl group, isobutyl group, secondary butyl group and tertiary butyl group.
- R and R' may be the same alkyl group or different alkyl groups.
- An alkoxy group has a structure in which an alkyl group (R) is bonded to an oxygen (O) atom, and is a monovalent functional group represented by the structural formula -OR.
- Alkoxy groups include methoxy, ethoxy, propoxy, butoxy and the like.
- the alkoxy group may be not only these linear alkoxy groups but also branched alkoxy groups such as isopropoxy, isobutoxy, secondary butoxy and tertiary butoxy.
- the aforementioned alkyl group includes methyl group, ethyl group, propyl group, butyl group and the like.
- the alkyl group may be not only these linear alkyl groups but also branched alkyl groups such as isopropyl group, isobutyl group, secondary butyl group and tertiary butyl group.
- Examples of the second raw material include trimethoxydimethylaminosilane ((CH 3 ) 2 NSi(OCH 3 ) 3 , abbreviation: TMDMAS) gas and trimethoxydiethylaminosilane ((C 2 H 5 ) 2 NSi(OCH 3 ) 3 ). gas, triethoxydimethylaminosilane (( CH3 ) 2NSi ( OC2H5 ) 3 ) gas, triethoxydiethylaminosilane (( C2H5 ) 2NSi ( OC2H5 ) 3 ) gas , and the like. Alkoxysilane gas can be used.
- Si contained in these gases has four bonds, three of the four bonds of Si are bonded to alkoxy groups, and the remaining four bonds of Si are An amino group is bound to one bond.
- the ratio of the number of amino groups to the number of alkoxy groups contained in the gas molecule is 1:3.
- the bond energy E 2 O between the alkoxy group and Si is higher than the bond energy EA between the amino group and Si. That is, an amino group has an active property that it is more likely to be eliminated from Si than an alkoxy group.
- the inert gas for example, nitrogen (N 2 ) gas, rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas can be used.
- nitrogen (N 2 ) gas rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, and xenon (Xe) gas can be used.
- Ar argon
- He helium
- Ne neon
- Xe xenon
- TDMAS gas when TDMAS gas is used as the second raw material, by performing this step under the processing conditions described later, methoxy groups (—OMe) are not eliminated from Si contained in the TDMAS gas, and dimethylamino groups are (-NMe 2 ) can be eliminated.
- adsorb (chemisorb) Si in a state where the dimethylamino group is eliminated and the bond with the methoxy group is maintained on the surface of the wafer 200 . That is, Si can be adsorbed to some of the adsorption sites on the surface of the wafer 200 in a state where three of the four bonds of Si are bonded to alkoxy groups.
- a reaction product generated when forming this layer constitutes, for example, a gaseous substance containing an amino group, and is discharged from the processing chamber 201 .
- the methoxy groups bonded to the Si adsorbed to the surface of the wafer 200 that is, the three bonds of the Si adsorbed to the surface of the wafer 200 are filled with methoxy groups. It becomes possible to inhibit the adsorption of atoms or molecules to the adsorbed Si.
- the methoxy groups bonded to the Si adsorbed to the surface of the wafer 200 act as steric hindrance to the adsorption sites (OH terminations) on the surface of the wafer 200 around the Si adsorbed to the surface of the wafer 200.
- the supply of the second raw material is continued until the adsorption reaction (chemisorption reaction) of Si to the surface of the wafer 200 is saturated. Even if the supply of the second raw material is continued in this way, the methoxy groups bonded to Si act as steric hindrance, so that Si can be discontinuously adsorbed on the surface of the wafer 200 . Specifically, Si can be adsorbed on the surface of the wafer 200 to a thickness of less than one atomic layer.
- the surface of the wafer 200 is covered with methoxy groups bonded to Si, as shown in FIG. is in a state in which the adsorption site (OH termination) is retained without being consumed.
- the layer composed of Si adsorbed to the surface of the wafer 200 becomes a discontinuous layer with a thickness of less than one atomic layer.
- the valve 243d is closed and the supply of the second raw material into the processing chamber 201 is stopped. Then, the inside of the processing chamber 201 is evacuated to remove gas and the like remaining in the processing chamber 201 from the inside of the processing chamber 201 (purge). At this time, the valves 243 e to 243 g are opened to supply inert gas into the processing chamber 201 . Inert gas acts as a purge gas.
- Step A After step B is completed, the first raw material is supplied to the wafer 200 in the processing chamber 201 , that is, the first layer formed on the wafer 200 .
- valve 243a is opened to allow the first raw material to flow into the gas supply pipe 232a.
- the flow rate of the first raw material is adjusted by the MFC 241a, supplied into the processing chamber 201 through the nozzle 249a, and exhausted through the exhaust port 231a.
- the first raw material is supplied to the wafer 200 (first raw material supply).
- the valves 243e to 243g are opened to supply the inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively. In some methods described below, the supply of the inert gas into the processing chamber 201 may be disabled.
- a gas having a molecular structure containing a halogen element bonded to silicon (Si) as a predetermined element that is, a halosilane gas
- Halogen elements include chlorine (Cl), fluorine (F), bromine (Br), iodine (I), and the like.
- a halosilane gas for example, a chlorosilane gas containing Si and Cl can be used.
- Examples of the first raw material include hexachlorodisilane (Si 2 Cl 6 , abbreviation: HCDS) gas, monochlorosilane (SiH 3 Cl, abbreviation: MCS) gas, dichlorosilane (SiH 2 Cl 2 , abbreviation: DCS) gas, and trichlorosilane (SiH 2 Cl 2 , abbreviation: DCS) gas.
- HCDS hexachlorodisilane
- MCS monochlorosilane
- DCS dichlorosilane
- DCS trichlorosilane
- a chlorosilane gas such as chlorosilane (SiHCl 3 , abbreviation: TCS) gas, tetrachlorosilane (SiCl 4 , abbreviation: STC) gas, or octachlorotrisilane (Si 3 Cl 8 , abbreviation: OCTS) gas can be used. These gases are oxygen-free gases. One or more of these can be used as the first raw material.
- the first raw material in addition to chlorosilane gas, for example, fluorosilane gas such as tetrafluorosilane (SiF 4 ) gas and difluorosilane (SiH 2 F 2 ) gas, tetrabromosilane (SiBr 4 ) gas, dibromosilane (SiH Bromosilane gas such as 2 Br 2 ) gas, iodosilane gas such as tetraiodosilane (SiI 4 ) gas, diiodosilane (SiH 2 I 2 ) gas and the like can also be used. These gases are oxygen-free gases. One or more of these can be used as the first raw material.
- fluorosilane gas such as tetrafluorosilane (SiF 4 ) gas and difluorosilane (SiH 2 F 2 ) gas
- tetrabromosilane (SiBr 4 ) gas tetrabromosilane (Si
- a gas containing Si and an amino group that is, an aminosilane gas can also be used.
- Examples of the first raw material include tetrakis(dimethylamino)silane (Si[N( CH3 ) 2 ] 4 , abbreviation: 4DMAS) gas, tris(dimethylamino)silane (Si[N( CH3 ) 2 ] 3H , abbreviation: 3DMAS) gas, bis(diethylamino)silane (Si[N ( C2H5 ) 2 ] 2H2 , abbreviation: BDEAS ) gas, bis(tertiarybutylamino)silane ( SiH2 [NH( C4 H 9 )] 2 , abbreviation: BTBAS) gas, and aminosilane gas such as (diisopropylamino)silane (SiH 3 [N(C 3 H 7 ) 2 ], abbreviation: DIPAS) gas can also be used. These gases are oxygen-free gases. One or more of these can be used as the first raw material
- this step is performed under the processing conditions described later to decompose a portion of the methoxy groups contained in the first layer formed on the wafer 200 to form Si. It becomes possible to eliminate the methyl group from some of the Os that are bound. In addition, it becomes possible to bond Si contained in the first raw material to O, which has a dangling bond due to elimination of the methyl group.
- the outermost surface of the wafer 200 as a base that is, on the first layer containing a component in which an alkoxy group is bonded to Si, is formed as a second layer containing a halogen element such as chlorine (Cl) with a predetermined thickness.
- the Si-containing layer containing a halogen element is formed on the outermost surface of the wafer 200 by physical adsorption or chemical adsorption of molecules of the first raw material, physical adsorption or chemical adsorption of molecules of a partially decomposed substance of the first raw material, and physical adsorption or chemical adsorption of molecules of the first raw material. It is formed by, for example, depositing Si by thermal decomposition of raw materials.
- the Si-containing layer containing a halogen element may be an adsorption layer (a physical adsorption layer or a chemisorption layer) of the molecules of the first raw material or the molecules of a substance obtained by partially decomposing the first raw material.
- Si contained in the first raw material is adsorbed on the outermost surface of the wafer 200 .
- the layer formed on the wafer 200 by performing this step includes Si—O—Si bonds, and Si A layer containing an alkoxy group (eg, methoxy group) bonded and a halogen group (eg, chloro group) bonded to Si is obtained.
- a reaction product generated when forming this layer constitutes, for example, a gaseous substance containing a halosilane or an amino group, and is discharged from the processing chamber 201 .
- valve 243a is closed and the supply of the first raw material into the processing chamber 201 is stopped. Then, the gas or the like remaining in the processing chamber 201 is removed from the processing chamber 201 (purge) by the same processing procedure as the purge in step B.
- Step C After step A is finished, an oxidant is supplied to the wafer 200 in the processing chamber 201 , ie, the first layer and the second layer formed on the wafer 200 .
- valve 243b is opened to allow the oxidant to flow into the gas supply pipe 232b.
- the flow rate of the oxidant is adjusted by the MFC 241b, supplied into the processing chamber 201 through the nozzle 249b, and exhausted through the exhaust port 231a.
- an oxidant is supplied to the wafer 200 (oxidant supply).
- the valves 243e to 243g are opened to supply the inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively. In some methods described below, the supply of the inert gas into the processing chamber 201 may be disabled.
- the oxidizing agent examples include oxygen (O 2 ) gas, plasma-excited O 2 gas (O 2 * ), ozone (O 3 ) gas, O 2 gas + hydrogen (H 2 ) gas, and water vapor (H 2 O). gas), nitric oxide (NO) gas, nitrous oxide (N 2 O) gas, and other oxygen (O)-containing gases can be used. One or more of these can be used as the oxidizing agent.
- the oxidizing agent When an O-containing gas is used as the oxidizing agent, at least a portion of the first layer and the second layer formed on the wafer 200 can be oxidized (modified) by performing this step under the processing conditions described later. It becomes possible. For example, an amino group or an alkoxy group can be removed from the first layer, and a hydroxyl group can be bonded to Si contained in the first layer. Further, for example, hydrogen can be desorbed from Si contained in the second layer, and a hydroxyl group can be bonded to the resulting dangling bond of Si.
- a layer formed by oxidizing the first layer and the second layer that is, a silicon oxide layer (SiO layer) containing Si and O is formed as a third layer on the outermost surface of the wafer 200 as a base.
- the layer (third layer) formed on the wafer 200 by performing this step includes Si—O—Si bonds, hydroxyl groups (—OH) bonded to Si, and The layers each contain halogen groups such as chloro groups bonded to Si.
- This halogen group functions as a reaction site with a nitriding agent supplied to the wafer 200 in step D, which will be described later, that is, a reaction site necessary for nitriding the third layer.
- a reaction product generated when forming this layer constitutes a gaseous substance containing, for example, an alkoxy group or an amino group, and is discharged from the processing chamber 201 .
- the valve 243b is closed to stop the supply of the oxidizing agent into the processing chamber 201. Then, the gas or the like remaining in the processing chamber 201 is removed from the processing chamber 201 (purge) by the same processing procedure as the purge in step B.
- Step D After step C is completed, a nitriding agent is supplied to the wafer 200 in the processing chamber 201, that is, the third layer formed on the wafer 200.
- a nitriding agent is supplied to the wafer 200 in the processing chamber 201, that is, the third layer formed on the wafer 200.
- valve 243c is opened to flow the nitriding agent into the gas supply pipe 232c.
- the nitriding agent is adjusted in flow rate by the MFC 241c, supplied into the processing chamber 201 through the nozzle 249c, and exhausted through the exhaust port 231a.
- a nitriding agent is supplied to the wafer 200 (nitriding agent supply).
- the valves 243e to 243g are opened to supply the inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively. In some methods described below, the supply of the inert gas into the processing chamber 201 may be disabled.
- nitriding agents include hydrogen nitride gases such as ammonia (NH 3 ) gas, diazene (N 2 H 2 ) gas, hydrazine (N 2 H 4 ) gas, and N 3 H 8 gas, that is, nitrogen (N) gas. and hydrogen (H) containing gas can be used. One or more of these can be used as the nitriding agent.
- hydrogen nitride gases such as ammonia (NH 3 ) gas, diazene (N 2 H 2 ) gas, hydrazine (N 2 H 4 ) gas, and N 3 H 8 gas, that is, nitrogen (N) gas.
- hydrogen (H) containing gas can be used.
- One or more of these can be used as the nitriding agent.
- N nitrogen
- C carbon
- H hydrogen
- N, C and H-containing gas for example, an amine-based gas or an organic hydrazine-based gas can be used.
- the N-, C- and H-containing gas is an N-containing gas, a C-containing gas, an H-containing gas, and an N- and C-containing gas.
- nitriding agents include monoethylamine (C 2 H 5 NH 2 , abbreviation: MEA) gas, diethylamine ((C 2 H 5 ) 2 NH, abbreviation: DEA) gas, triethylamine ((C 2 H 5 ) 3 N , abbreviation: TEA) gas, monomethylamine (CH 3 NH 2 , abbreviation: MMA) gas, dimethylamine ((CH 3 ) 2 NH, abbreviation: DMA) gas, trimethylamine ((CH 3 ) 3 Methylamine-based gas such as N (abbreviation: TMA) gas, monomethylhydrazine ((CH 3 )HN 2 H 2 , abbreviation: MMH) gas, dimethylhydrazine ((CH 3 ) 2 N 2 H 2 , abbreviation: DMH) gas An organic hydrazine-based gas such as a gas, trimethylhydrazine ((CH 3 ) 2 N 2
- N- and H-containing gas As the nitriding agent, it is possible to nitridate (modify) at least part of the third layer formed on the wafer 200 by performing this step under the processing conditions described later. Become. For example, a halogen group such as a chloro group contained in the third layer is reacted with an N- and H-containing gas to eliminate the halogen group from the third layer, and the halogen group is eliminated to have a dangling bond. It becomes possible to bind N-containing groups such as amino groups (--NH 2 ) formed by decomposition of N- and H-containing gas to the different Si.
- N-containing groups such as amino groups (--NH 2 ) formed by decomposition of N- and H-containing gas
- a layer obtained by nitriding the third layer that is, a silicon oxynitride layer (SiON layer) containing Si, O and N is formed as a fourth layer on the outermost surface of the wafer 200 as a base. .
- SiON layer silicon oxynitride layer
- the nitridation reaction of the third layer in this step can proceed due to the presence of halogen groups on the surface of the third layer. If the entire surface of the third layer is OH-terminated and no halogen groups are present on the surface of the third layer, it can be said that it is difficult to nitride the third layer even if this step is performed. . As shown in FIG.
- the layer (fourth layer) formed on the wafer 200 by performing this step includes Si—O—Si bonds, hydroxyl groups (—OH) bonded to Si, and The layers each contain N-containing groups such as amino groups (—NH 2 ) bonded to Si.
- a reaction product generated when forming this layer constitutes a gaseous substance containing hydrogen halide such as HCl, for example, and is discharged from the processing chamber 201 .
- the valve 243b is closed and the supply of the nitriding agent into the processing chamber 201 is stopped. Then, the gas remaining in the processing chamber 201 is removed from the processing chamber 201 (purge) by the same processing procedure as the purge in step A.
- a film is formed on the surface of the wafer 200 by performing the above steps B, A, C, and D non-simultaneously, that is, by performing cycles in this order without synchronization a predetermined number of times (n times, where n is an integer equal to or greater than 1).
- a silicon oxynitride film SiON film
- the above cycle is preferably repeated multiple times. That is, the thickness of the SiON layer formed per cycle is made thinner than the desired film thickness, and the above-described steps are repeated until the thickness of the SiON film formed by stacking the SiON layers reaches the desired thickness. It is preferred to repeat the cycle multiple times.
- a silicon oxycarbonitride layer (SiOCN layer) can be formed as the fourth layer.
- a silicon oxycarbonitride film (SiOCN film) can be formed on the surface of the wafer 200 .
- processing conditions in each of the above steps are examples.
- the expression of a numerical range such as “1 to 2666 Pa” in this specification means that the lower limit and the upper limit are included in the range. Therefore, for example, “1 to 2666 Pa” means “1 Pa or more and 2666 Pa or less”.
- the processing temperature in this specification means the temperature of the wafer 200
- the processing pressure means the pressure in the processing chamber 201, which is the space in which the wafer 200 exists.
- the gas supply flow rate: 0 slm means a case where the gas is not supplied.
- Second raw material supply flow rate 0.01 to 2 slm, preferably 0.1 to 1 slm
- Second raw material supply time 1 to 120 seconds, preferably 1 to 60 seconds
- Inert gas supply flow rate 0 to 30 slm
- Treatment pressure: 1 to 2666 Pa, preferably 67 to 1333 Pa are exemplified.
- First raw material supply flow rate 0.01 to 2 slm, preferably 0.1 to 1 slm
- First raw material supply time 1 to 120 seconds, preferably 1 to 60 seconds.
- Other processing conditions can be the same as the processing conditions in step B.
- Oxidant supply flow rate 0.1 to 10 slm Oxidant supply time: 1 to 120 seconds, preferably 1 to 60 seconds
- Treatment pressure: 1 to 4000 Pa, preferably 1 to 3000 Pa are exemplified.
- Other processing conditions can be the same as the processing conditions in step B.
- Nitriding agent supply flow rate 0.1 to 10 slm
- Nitriding agent supply time 1 to 120 seconds, preferably 1 to 60 seconds
- Treatment pressure 1 to 4000 Pa, preferably 1 to 3000 Pa
- Other processing conditions can be the same as the processing conditions in step B.
- the concentration of nitrogen contained in the SiON film formed on the wafer 200 can be set to a desired value. becomes possible.
- the concentration of nitrogen contained in the SiON film formed on the wafer 200 can be reduced. becomes.
- the concentration of nitrogen contained in the SiON film formed on the wafer 200 can be lowered. It becomes possible.
- the nitrogen concentration contained in the SiON film formed on the wafer 200 can be reduced.
- step A by making the processing pressure in step A lower than the processing pressure in step B, it is possible to reduce the concentration of nitrogen contained in the SiON film formed on the wafer 200 .
- the concentration of nitrogen contained in the SiON film formed on the wafer 200 can be set to a desired value. becomes possible.
- the concentration of nitrogen contained in the SiON film formed on the wafer 200 can be reduced. becomes.
- the concentration of nitrogen contained in the SiON film formed on the wafer 200 can be lowered. It becomes possible.
- an inert gas as a purge gas is supplied into the processing chamber 201 from each of the nozzles 249a to 249c, and exhausted from the exhaust port 231a.
- the inside of the processing chamber 201 is purged, and gases remaining in the processing chamber 201, reaction by-products, and the like are removed from the inside of the processing chamber 201 (afterpurge).
- the atmosphere in the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure recovery).
- the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafer 200 is unloaded from the reaction tube 203 from the lower end of the manifold 209 while being supported by the boat 217 (boat unloading). After the boat is unloaded, the shutter 219s is moved and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter closed). The processed wafers 200 are carried out of the reaction tube 203 and then taken out from the boat 217 (wafer discharge).
- a cycle of performing the above steps B, A, C, and D in this order is repeated a predetermined number of times so that the concentration (composition ratio) of nitrogen in the SiON film formed on the wafer 200 is set to a desired value.
- concentration ratio concentration ratio
- step A if step A is not performed and steps B, C, and D are repeated in this order for a predetermined number of times, the nitriding reaction does not progress easily, and the film formed on the wafer 200 contains N. As a result, a silicon oxide film (SiO film) containing almost no N is formed on the wafer 200 . This is because N contained in the gas containing N and H, which is a nitriding agent, is less likely to bond to Si bonds contained in the Si-containing layer formed on the wafer 200 by performing step B. Conceivable.
- the surface of the Si-containing layer formed on the wafer 200 has a halogen group capable of reacting with the N- and H-containing gas even after the oxidant is supplied.
- N it is possible to include N in the layer formed on the wafer 200 and form a SiON film on the wafer 200 to which N is added at a desired concentration. .
- step B is not performed and a cycle of performing steps A, C, and D in this order is repeated a predetermined number of times, an excessive amount of N will be incorporated into the film formed on the wafer 200, resulting in It becomes difficult to reduce the nitrogen concentration in the SiON film formed on 200 to a desired value.
- the Si-containing layer formed by performing Step A has high reactivity with the N- and H-containing gases, and even if the processing conditions in Steps C and D are changed over a wide range, the Si-containing layer is formed on the wafer 200. This is probably because it is difficult to suppress the addition of N into the Si-containing layer.
- step B by performing step B prior to step A, the addition of N to the Si-containing layer formed on the wafer 200 is appropriately suppressed, and the Si-containing layer formed on the wafer 200 is It becomes possible to reduce the nitrogen concentration in the SiON film to a desired value.
- step B by continuing to supply the second raw material until the adsorption reaction (chemisorption reaction) of the second raw material Si on the surface of the wafer 200 is saturated, Si and oxygen contained in the first layer can be maximized and the nitrogen concentration in the SiON film formed on the wafer 200 can be reduced.
- adsorption reaction chemisorption reaction
- step B the amino group is removed from the Si contained in the second raw material without removing the alkoxy group, and the Si in which the amino group is removed and the bond with the alkoxy group is maintained is transferred to the wafer 200.
- the action of the alkoxy group bonded to the Si can inhibit the adsorption of atoms or molecules to the adsorption sites on the surface of the wafer 200 on the Si adsorbed on the surface of the wafer 200 and its surroundings. It becomes possible.
- the layer composed of Si adsorbed to the surface of the wafer 200 can be made into a discontinuous layer with a thickness of less than one atomic layer.
- the wafer in-plane film thickness uniformity and step coverage of the SiON film formed on the wafer 200 can be improved, and the film can be made conformal.
- a gas such as 3DMAS gas in which an amino group is bonded to the central atom Si and no alkoxy group is bonded is used as the raw material gas, the effect of the alkoxy group (methoxy group) in this embodiment is obtained.
- the wafer in-plane film thickness uniformity and step coverage of the SiON film formed on the wafer 200 are degraded.
- step B the Si-containing layer formed on the wafer 200 is formed on the surface of the wafer 200 by preventing the amino groups released from the Si contained in the second raw material from being adsorbed on the surface of the wafer 200. A layer with few impurities can be obtained. As a result, the SiON film formed on the wafer 200 can be a film with excellent processing resistance.
- steps C and D amino groups, methoxy groups, and halogen groups are eliminated from the layer to be modified, so that the layer after modification is a layer with less impurities such as C and halogen elements. becomes possible.
- the SiON film formed on the wafer 200 can be a film with excellent processing resistance.
- steps C and D an oxidizing agent and a nitriding agent are supplied in a non-plasma atmosphere to avoid plasma damage to the film formed on the wafer 200, its underlying layer, members in the processing chamber 201, and the like. It becomes possible to
- the substrate processing sequence in this aspect can be modified as in the following modifications. These modifications can be combined arbitrarily. Unless otherwise specified, the processing procedures and processing conditions in each step of each modification can be the same as the processing procedures and processing conditions in each step of the above-described modes.
- the first layer having the halogen termination is formed on the wafer 200 by supplying the first raw material in advance. Since the substitution reaction with the amino groups contained in the second raw material is unlikely to occur in the halogen-terminated first layer, the ratio of the halogen-terminated first layer, which easily reacts with the N- and H-containing gas as the nitriding agent, is It becomes relatively larger than the ratio of the second layer formed from the second raw material, and it becomes easier to increase the nitrogen concentration in the SiON film formed on the wafer 200 than in the above-described mode.
- the reaction between the N- and H-containing gas and the first layer and the second layer in step D is more likely to occur than in the above-described embodiment.
- the oxidizing agent in step C it becomes easier to adjust the nitrogen concentration in the SiON film formed on the wafer 200 so as to be relatively high.
- the oxidizing agent is added in step C prior to step D as in the above-described embodiment and modification 1.
- a mode of supplying to the wafer 200 is more preferable.
- the same effect as the above-described mode can be obtained in this modified example as well.
- the nitrogen concentration in the SiON film formed on the wafer 200 is adjusted to be relatively higher than in the above-described mode and modification 1. becomes easier.
- the present modified example as in the second modified example, it is possible to increase the formation rate of the SiON film formed on the wafer 200 compared to the above-described mode and the first modified example.
- the nitriding agent may be supplied (preflowed) to the wafer 200 before performing the predetermined number of cycles.
- the conditions for supplying the nitriding agent in the preflow and the conditions for supplying the nitriding agent in step D may be different. Also, the nitriding agent in the preflow and the nitriding agent in step D may be of the same type of gas or may be of different types.
- step B the supply of the second raw material may be stopped before the adsorption reaction of the second raw material on the surface of the wafer 200 is saturated.
- the ratio of Si and oxygen contained in the Si-containing layer formed in step B is adjusted, and the wafer
- the nitrogen concentration in the SiON film formed on 200 can be controlled.
- the nitrogen concentration in the SiON film formed on the wafer 200 can be adjusted to increase by shortening the supply time of the second raw material in step B. It becomes possible.
- the oxidizing agent and nitriding agent may be supplied by plasma excitation.
- the processing procedures and processing conditions in these cases can be the same as those in steps C and D of the above-described mode. Even in these cases, effects similar to those of the above embodiments can be obtained.
- the predetermined element constituting the central atom X contained in the raw material may be, for example, a metal element such as aluminum (Al), titanium (Ti), zirconium (Zr), hafnium (Hf) or lanthanum (La). Further, the predetermined element may be, for example, an element of the same Group 14 element as Si, or may be a Group 4 element.
- the second raw material has, for example, an amino group bonded to one bond of an atom of the predetermined element, and an alkoxy group bonded to the remaining three bonds. It preferably has a molecular structure in which groups are bonded.
- the processing procedures and processing conditions in these cases can be the same as those in the above embodiments. Also in these cases, the same effects as those of the above embodiments can be obtained.
- the recipes used for each process are individually prepared according to the contents of the process and stored in the storage device 121c via the telecommunication line or the external storage device 123. Then, when starting each process, it is preferable that the CPU 121a appropriately selects an appropriate recipe from among the plurality of recipes stored in the storage device 121c according to the process content.
- a single substrate processing apparatus can form films having various film types, composition ratios, film qualities, and film thicknesses with good reproducibility.
- the burden on the operator can be reduced, and each process can be started quickly while avoiding operational errors.
- the recipes described above are not limited to the case of newly creating them, and for example, they may be prepared by modifying existing recipes that have already been installed in the substrate processing apparatus.
- the changed recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium recording the recipe.
- an existing recipe already installed in the substrate processing apparatus may be directly changed by operating the input/output device 122 provided in the existing substrate processing apparatus.
- an example of forming a film using a batch-type substrate processing apparatus that processes a plurality of substrates at once has been described.
- the present disclosure is not limited to the embodiments described above, and can be suitably applied, for example, to the case of forming a film using a single substrate processing apparatus that processes one or several substrates at a time.
- an example of forming a film using a substrate processing apparatus having a hot wall type processing furnace has been described.
- the present disclosure is not limited to the above embodiments, and can be suitably applied to the case of forming a film using a substrate processing apparatus having a cold wall type processing furnace.
- the above aspects and modifications can be used in combination as appropriate.
- the processing procedure and processing conditions at this time can be, for example, the same as the processing procedures and processing conditions in the above-described modes and modifications.
- sample 1 the substrate processing apparatus described above is used, and a cycle of supplying TMDMAS gas as the second raw material, HCDS gas as the first raw material, O2 gas as the oxidizing agent, and NH3 gas as the nitriding agent to the wafer in this order is performed.
- a SiON film was formed on the wafer by repeating the process a predetermined number of times.
- the processing conditions in each step were set to predetermined conditions within the range of processing conditions described in the above embodiments.
- a SiON film was formed on a wafer by performing a cycle of supplying the first raw material, the second raw material, the oxidizing agent, and the nitriding agent in this order to the wafer using the substrate processing apparatus described above a predetermined number of times. .
- the processing conditions and the number of cycles performed in each step were the same as those in the preparation of Sample 1.
- a SiON film was formed on a wafer by performing a cycle of supplying the first raw material, the oxidizing agent, and the nitriding agent in this order to the wafer using the substrate processing apparatus described above a predetermined number of times.
- the processing conditions and the number of cycles performed in each step were the same as those in the preparation of Sample 1.
- the wafer in-plane average film thickness (Thick.), refractive index (R.I.), and nitrogen concentration (N concentration) of the SiON film of each sample were measured.
- the refractive index is used as an index indicating the Si concentration in the SiON film, and the higher the refractive index, the higher the Si concentration.
- the SiON films of Samples 1 and 2 which were produced using both the first source material and the second source material, were superior to those of Sample 3, which was fabricated using only the first source material without using the second source material. It was confirmed that the N concentration was lower than that of the film.
- the SiON film of Sample 1 which was fabricated by supplying the second raw material, the first raw material, the oxidizing agent, and the nitriding agent in this order, supplied the first raw material, the second raw material, the oxidizing agent, and the nitriding agent in this order. It has been confirmed that the N concentration is lower than that of the SiON film of the sample 2 manufactured by doing so.
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Abstract
Description
(a)基板に対して所定元素を含む第1原料を供給する工程と、
(b)前記基板に対して、前記第1原料とは分子構造が異なり、前記所定元素及び酸素を含む第2原料を供給する工程と、
(c)前記基板に対して酸化剤を供給する工程と、
(d)前記基板に対して窒化剤を供給する工程と、
を含むサイクルを所定回数行うことで、前記基板上に、前記所定元素、酸素及び窒素を含む膜を形成する工程を有する技術が提供される。
以下、本開示の一態様について、主に、図1~図4、図5A~図5Eを参照しながら説明する。なお、以下の説明において用いられる図面は、いずれも模式的なものであり、図面上の各要素の寸法の関係、各要素の比率等は、現実のものとは必ずしも一致していない。また、複数の図面の相互間においても、各要素の寸法の関係、各要素の比率等は必ずしも一致していない。
図1に示すように、処理炉202は温度調整器(加熱部)としてのヒータ207を有する。ヒータ207は円筒形状であり、保持板に支持されることにより垂直に据え付けられている。ヒータ207は、ガスを熱で活性化(励起)させる活性化機構(励起部)としても機能する。
上述の基板処理装置を用い、半導体装置の製造工程の一工程として、基板としてのウエハ200に対し処理を行うシーケンス例、すなわち、ウエハ200上に膜を形成する成膜シーケンス例について、主に、図4を用いて説明する。以下の説明において、基板処理装置を構成する各部の動作はコントローラ121により制御される。
ウエハ200に対して所定元素を含む第1原料を供給するステップAと、
ウエハ200に対して、第1原料とは分子構造が異なり、所定元素及び酸素を含む第2原料を供給するステップBと、
ウエハ200に対して酸化剤を供給するステップCと、
ウエハ200に対して窒化剤を供給するステップDと、
を含むサイクルを所定回数(n回、nは1以上の整数)行うことで、ウエハ200上に、所定元素、酸素及び窒素を含む膜を形成する。
各サイクルにおいて、ステップAおよびBの後にステップCおよびDを行う場合、具体的には、ステップA,B,C,Dを非同時に行う場合、より具体的にはステップB,A,C,Dをこの順に行う場合を示している。
複数枚のウエハ200がボート217に装填(ウエハチャージ)された後、シャッタ開閉機構115sによりシャッタ219sが移動させられて、マニホールド209の下端開口が開放される(シャッタオープン)。その後、図1に示すように、複数枚のウエハ200を支持したボート217は、ボートエレベータ115によって持ち上げられて処理室201内へ搬入(ボートロード)される。この状態で、シールキャップ219は、Oリング220bを介してマニホールド209の下端をシールした状態となる。
ボートロードが終了した後、処理室201内、すなわち、ウエハ200が存在する空間が所望の圧力(真空度)となるように、真空ポンプ246によって真空排気(減圧排気)される。この際、処理室201内の圧力は圧力センサ245で測定され、この測定された圧力情報に基づきAPCバルブ244がフィードバック制御される(圧力調整)。また、処理室201内のウエハ200が所望の処理温度となるように、ヒータ207によって加熱される。この際、処理室201内が所望の温度分布となるように、温度センサ263が検出した温度情報に基づきヒータ207への通電具合がフィードバック制御される(温度調整)。また、回転機構267によるウエハ200の回転を開始する。処理室201内の排気、ウエハ200の加熱および回転は、いずれも、少なくともウエハ200に対する処理が終了するまでの間は継続して行われる。
その後、以下のステップB,A,C,Dを順次実行する。
このステップでは、処理室201内のウエハ200に対して、第2原料を供給する。
ステップBが終了したら、処理室201内のウエハ200、すなわち、ウエハ200上に形成された第1層に対して第1原料を供給する。
ステップAが終了した後、処理室201内のウエハ200、すなわち、ウエハ200上に形成された第1層および第2層に対して酸化剤を供給する。
ステップCが終了した後、処理室201内のウエハ200、すなわち、ウエハ200上に形成された第3層に対して窒化剤を供給する。
上述のステップB,A,C,Dを非同時に、すなわち、同期させることなくこの順に行うサイクルを所定回数(n回、nは1以上の整数)行うことにより、ウエハ200の表面上に、膜として、例えば、シリコン酸窒化膜(SiON膜)を形成することができる。上述のサイクルは、複数回繰り返すことが好ましい。すなわち、1サイクルあたりに形成されるSiON層の厚さを所望の膜厚よりも薄くし、SiON層を積層することで形成されるSiON膜の厚さが所望の厚さになるまで、上述のサイクルを複数回繰り返すことが好ましい。なお、窒化剤として、N,C及びH含有ガスを用いる場合、第4層として、例えば、シリコン酸炭窒化層(SiOCN層)を形成することもでき、上述のサイクルを所定回数行うことで、ウエハ200の表面上に、膜として、例えば、シリコン酸炭窒化膜(SiOCN膜)を形成することもできる。
第2原料供給流量:0.01~2slm、好ましくは0.1~1slm
第2原料供給時間:1~120秒、好ましくは1~60秒
不活性ガス供給流量:0~30slm
処理温度:550~700℃、好ましくは600~650℃
処理圧力:1~2666Pa、好ましくは67~1333Pa
が例示される。
第1原料供給流量:0.01~2slm、好ましくは0.1~1slm
第1原料供給時間:1~120秒、好ましくは1~60秒
が例示される。他の処理条件は、ステップBにおける処理条件と同様とすることができる。
酸化剤供給流量:0.1~10slm
酸化剤供給時間:1~120秒、好ましくは1~60秒
処理圧力:1~4000Pa、好ましくは1~3000Pa
が例示される。他の処理条件は、ステップBにおける処理条件と同様とすることができる。
窒化剤供給流量:0.1~10slm
窒化剤供給時間:1~120秒、好ましくは1~60秒
処理圧力:1~4000Pa、好ましくは1~3000Pa
が例示される。他の処理条件は、ステップBにおける処理条件と同様とすることができる。
ウエハ200上への所望の厚さの膜の形成が完了した後、ノズル249a~249cのそれぞれから、パージガスとしての不活性ガスを処理室201内へ供給し、排気口231aより排気する。これにより、処理室201内がパージされ、処理室201内に残留するガスや反応副生成物等が処理室201内から除去される(アフターパージ)。その後、処理室201内の雰囲気が不活性ガスに置換され(不活性ガス置換)、処理室201内の圧力が常圧に復帰される(大気圧復帰)。
その後、ボートエレベータ115によりシールキャップ219が下降され、マニホールド209の下端が開口される。そして、処理済のウエハ200が、ボート217に支持された状態でマニホールド209の下端から反応管203の外部に搬出(ボートアンロード)される。ボートアンロードの後は、シャッタ219sが移動させられ、マニホールド209の下端開口がOリング220cを介してシャッタ219sによりシールされる(シャッタクローズ)。処理済のウエハ200は、反応管203の外部に搬出された後、ボート217より取り出される(ウエハディスチャージ)。
本態様によれば、以下に示す1つ又は複数の効果が得られる。
本態様における基板処理シーケンスは、以下に示す変形例のように変更することができる。これらの変形例は、任意に組み合わせることができる。特に説明がない限り、各変形例の各ステップにおける処理手順、処理条件は、上述の態様の各ステップにおける処理手順、処理条件と同様とすることができる。
以下に示すガス供給シーケンスのように、各サイクルでは、ステップA,B,C,Dをこの順に行うようにしてもよい。
以下に示すガス供給シーケンスのように、各サイクルでは、ステップA,B,D,Cをこの順に行うようにしてもよい。
以下に示すガス供給シーケンスのように、各サイクルでは、ステップB,A,D,Cをこの順に行うようにしてもよい。
以下に示すガス供給シーケンスのように、サイクルを所定回数行う前に、ウエハ200に対して窒化剤を供給(プリフロー)するようにしてもよい。
窒化剤→(第1原料→第2原料→酸化剤→窒化剤)×n
窒化剤→(第2原料→第1原料→窒化剤→酸化剤)×n
窒化剤→(第1原料→第2原料→窒化剤→酸化剤)×n
各サイクルでは、ステップAにおける第1原料が供給される期間と、ステップBにおける第2原料が供給される期間と、の少なくとも一部を重ねるようにしてもよい。本変形例においても、上述の態様と同様の効果が得られる。また、本変形例においては、サイクルタイムを短縮し、製膜処理のスループットを向上させることが可能となる。
ステップBでは、第2原料のウエハ200の表面への吸着反応が飽和する前に、第2原料の供給を停止するようにしてもよい。第2原料の吸着反応が飽和しない状態(不飽和状態)において第2原料の供給時間を調整することにより、ステップBにおいて形成されるSi含有層に含まれるSiや酸素の比率を調整し、ウエハ200上に形成されるSiON膜中の窒素濃度を制御することが可能となる。
例えば、第2原料の吸着反応が飽和しない状態において、ステップBにおける第2原料の供給時間を短くすることにより、ウエハ200上に形成されるSiON膜中における窒素濃度を高める方向に調整することが可能となる。
以上、本開示の態様を具体的に説明した。しかしながら、本開示は上述の態様に限定されるものではなく、その要旨を逸脱しない範囲で種々変更可能である。
Claims (19)
- (a)基板に対して所定元素を含む第1原料を供給する工程と、
(b)前記基板に対して、前記第1原料とは分子構造が異なり、前記所定元素及び酸素を含む第2原料を供給する工程と、
(c)前記基板に対して酸化剤を供給する工程と、
(d)前記基板に対して窒化剤を供給する工程と、
を含むサイクルを所定回数行うことで、前記基板上に、前記所定元素、酸素及び窒素を含む膜を形成する工程を有する半導体装置の製造方法。 - 前記サイクルでは、(a)(b)(c)(d)を非同時に行う請求項1に記載の半導体装置の製造方法。
- 前記サイクルでは、(a)(b)(c)(d)をこの順に行う請求項2に記載の半導体装置の製造方法。
- 前記サイクルでは、(b)(a)(c)(d)をこの順に行う請求項2に記載の半導体装置の製造方法。
- 前記サイクルでは、(a)(b)(d)(c)をこの順に行う請求項2に記載の半導体装置の製造方法。
- 前記サイクルでは、(b)(a)(d)(c)をこの順に行う請求項2に記載の半導体装置の製造方法。
- 前記サイクルを前記所定回数行う前に、前記基板に対して前記窒化剤を供給する工程を有する請求項1~6のいずれか1項に記載の半導体装置の製造方法。
- 前記第2原料は、前記所定元素の原子に結合したアルコキシ基を含む分子構造を有している請求項1~7のいずれか1項に記載の半導体装置の製造方法。
- 前記第2原料は、前記所定元素の原子の少なくとも1つの結合手にアミノ基が結合しており、残りの結合手にアルコキシ基が結合している分子構造を有している請求項1~7のいずれか1項に記載の半導体装置の製造方法。
- 前記所定元素はシリコンである請求項8又は9に記載の半導体装置の製造方法。
- (b)では、前記所定元素の原子から前記アルコキシ基が脱離することなく、前記所定元素の原子に結合した他の少なくとも1つの基が脱離する条件であって、前記少なくとも1つの基が脱離し前記アルコキシ基との結合が維持された状態の前記所定元素の原子が、前記基板の表面に吸着する条件下で、前記第2原料が前記基板に対して供給される請求項8~10のいずれか1項に記載の半導体装置の製造方法。
- 前記第1原料は、前記所定元素の原子に結合したハロゲン元素を含む分子構造を有している請求項1~11のいずれか1項に記載の半導体装置の製造方法。
- 前記膜に含ませる窒素の濃度を所定の値とするように、(a)における前記第1原料の供給時間に対する(b)における前記第2原料の供給時間の比率を設定する請求項1~12のいずれか1項に記載の半導体装置の製造方法。
- 前記膜に含ませる窒素の濃度を所定の値とするように、(a)における前記基板が存在する空間の圧力に対する(b)における前記基板が存在する空間の圧力の比率を設定する請求項1~13のいずれか1項に記載の半導体装置の製造方法。
- 前記膜に含ませる窒素の濃度を所定の値とするように、(a)における前記第1原料の供給流量に対する(b)における前記第2原料の供給流量の比率を設定する請求項1~13のいずれか1項に記載の半導体装置の製造方法。
- (a)では、前記第2原料の前記基板の表面への吸着反応が飽和するまで、前記第2原料の供給を継続する請求項1~15のいずれか1項に記載の半導体装置の製造方法。
- (a)では、前記第2原料の前記基板の表面への吸着反応が飽和する前に、前記第2原料の供給を停止する請求項1~15のいずれか1項に記載の半導体装置の製造方法。
- 基板が処理される処理室と、
前記処理室内の前記基板に対して、所定元素を含む第1原料を供給する第1原料供給系と、
前記処理室内の前記基板に対して、前記第1原料とは分子構造が異なり、前記所定元素及び酸素を含む第2原料を供給する第2原料供給系と、
前記処理室内の前記基板に対して、酸化剤を供給する酸化剤供給系と
前記処理室内の前記基板に対して、窒化剤を供給する窒化剤供給系と
(a)前記基板に対して前記第1原料を供給する処理と、(b)前記基板に対して前記第2原料を供給する処理と、(c)前記基板に対して前記酸化剤を供給する処理と、(d)前記基板に対して前記窒化剤を供給する処理と、を含むサイクルを所定回数行うことで、前記基板上に、前記所定元素、酸素及び窒素を含む膜を形成する処理を行わせるように、前記第1原料供給系、前記第2原料供給系、前記酸化剤供給系、および前記窒化剤供給系を制御することが可能なように構成される制御部と、
を有する基板処理装置。 - 基板処理装置の処理室内において、
(a)基板に対して所定元素を含む第1原料を供給する手順と、
(b)前記基板に対して、前記第1原料とは分子構造が異なり、前記所定元素及び酸素を含む第2原料を供給する手順と、
(c)前記基板に対して酸化剤を供給する手順と、
(d)前記基板に対して窒化剤を供給する手順と、
を含むサイクルを所定回数行うことで、前記基板上に、前記所定元素、酸素及び窒素を含む膜を形成する手順を、
コンピュータによって前記基板処理装置に実行させるプログラム。
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EP21927925.4A EP4300546A1 (en) | 2021-02-26 | 2021-02-26 | Method for producing semiconductor device, substrate processing apparatus, and program |
PCT/JP2021/007506 WO2022180825A1 (ja) | 2021-02-26 | 2021-02-26 | 半導体装置の製造方法、基板処理装置、およびプログラム |
CN202180089359.9A CN116802776A (zh) | 2021-02-26 | 2021-02-26 | 半导体器件的制造方法、衬底处理装置及程序 |
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