Classifications

• • 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
  • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
  • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
  • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
  • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
  • H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
• • 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
  • H01L21/04—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
  • 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
  • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
  • H01L21/321—After treatment
  • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
  • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
  • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
• • 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
  • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
  • C23C16/45523—Pulsed gas flow or change of composition over time
  • C23C16/45525—Atomic layer deposition [ALD]
  • 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
• • 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
  • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
  • C23C16/45523—Pulsed gas flow or change of composition over time
  • C23C16/45525—Atomic layer deposition [ALD]
  • C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
  • C23C16/45546—Atomic layer deposition [ALD] characterized by the apparatus specially adapted for a substrate stack in the ALD reactor
• • 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
  • C23C16/56—After-treatment
• • 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
  • H01L21/04—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
  • 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
  • H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
  • H01L21/2003—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy characterised by the substrate
  • H01L21/2015—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy characterised by the substrate the substrate being of crystalline semiconductor material, e.g. lattice adaptation, heteroepitaxy
• • 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
  • H01L21/04—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
  • 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
  • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
  • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
  • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
  • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
  • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
  • H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
• • 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
  • H01L21/04—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
  • 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
  • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
  • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
  • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
  • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
  • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
  • H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
  • H01L21/28562—Selective deposition

Definitions

• This disclosure relates to a substrate processing method, a semiconductor device manufacturing method, a program, and a substrate processing apparatus.
• a process of forming a metal film on a substrate may be performed (see, for example, Patent Document 1).
• This disclosure provides technology that can improve the properties of a film formed on a substrate.
• FIG. 1 is a schematic vertical cross-sectional view of a vertical processing furnace of a substrate processing apparatus according to one embodiment of the present disclosure.
• FIG. 2 is a schematic cross-sectional view taken along line AA in FIG.
• FIG. 3 is a schematic configuration diagram of a controller of a substrate processing apparatus according to one embodiment of the present disclosure, and is a block diagram showing a control system of the controller.
• FIG. 4 is a diagram illustrating a substrate processing process according to one embodiment of the present disclosure.
• 5A to 5D are cross-sectional views for explaining the state of a substrate in a substrate processing step according to one embodiment of the present disclosure.
• FIG. 6 illustrates a modified example of a substrate processing process according to an embodiment of the present disclosure.
• FIGS. 7A to 7F are diagrams illustrating modified examples of the film forming process according to one embodiment of the present disclosure.
• 8A to 8F are diagrams illustrating modified examples of the etching process according to one embodiment of the present disclosure.
• FIG. 9 illustrates a modified example of a substrate processing process according to an embodiment of the present disclosure.
• FIG. 10 is a top view illustrating a modified example of the substrate processing apparatus according to one aspect of the present disclosure.
• the processing furnace 202 has a heater 207 as a heating system (temperature adjustment unit).
• the heater 207 has a cylindrical shape.
• the heater 207 also functions as an activation mechanism (excitation unit) that activates (excites) gas by heat.
• a reaction tube 203 is disposed concentrically with the heater 207 inside the heater 207.
• the reaction tube 203 is made of a heat-resistant material such as quartz (SiO 2 ) or silicon carbide (SiC), and is formed in a cylindrical shape with a closed upper end and an open lower end.
• a manifold 209 is disposed concentrically with the reaction tube 203 below the reaction tube 203.
• the manifold 209 is made of a metal such as stainless steel (SUS), and is formed in a cylindrical shape with an open upper end and a closed lower end. The upper end of the manifold 209 is engaged with the lower end of the reaction tube 203, and is configured to support the reaction tube 203.
• An O-ring 220a is provided between the manifold 209 and the reaction tube 203 as a seal member.
• the reaction tube 203 is installed vertically like the heater 207.
• the reaction tube 203 and the manifold 209 mainly constitute a processing vessel (reaction vessel).
• a processing chamber 201 is formed in a cylindrical hollow portion of the processing vessel.
• the processing chamber 201 is configured to be capable of accommodating a plurality of wafers 200 as substrates.
• Nozzles 249a and 249b are provided in the processing chamber 201 so as to penetrate the side wall of the manifold 209.
• Gas supply pipes (pipes) 232a and 232b are connected to the nozzles 249a and 249b, respectively.
• Gas supply pipes 232a, 232b are provided with mass flow controllers (MFCs) 241a, 241b, which are flow rate controllers (flow rate control parts), and valves 243a, 243b, which are on-off valves, in order from the upstream side.
• MFCs mass flow controllers
• Gas supply pipes 232c, 232d which supply inert gas, are connected to gas supply pipes 232a, 232b downstream of valves 243a, 243b.
• Gas supply pipes 232c, 232d are provided with MFCs 241c, 241d and valves 243c, 243d, in order from the upstream side, in gas supply pipes 232c, 232d, respectively.
• the nozzles 249a and 249b are provided in a circular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, and are arranged to rise upward in the loading direction of the wafers 200 along the inner wall of the reaction tube 203 from the lower part to the upper part.
• Gas supply holes 250a and 250b for supplying gas are provided on the side of the nozzles 249a and 249b.
• the gas supply holes 250a and 250b are each open toward the center of the reaction tube 203, making it possible to supply gas toward the wafers 200.
• a plurality of gas supply holes 250a and 250b are provided from the lower part to the upper part of the reaction tube 203.
• a raw material gas containing a halogen element is supplied into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.
• a reactive gas that reacts with the raw material 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 reducing gas can be used as the reactive gas.
• Inert gas is supplied from gas supply pipes 232c and 232d into the processing chamber 201 via MFCs 241c and 241d, valves 243c and 243d, gas supply pipes 232a and 232b, and nozzles 249a and 249b, respectively.
• the raw material gas supply system is mainly composed of the gas supply pipe 232a, the MFC 241a, and the valve 243a.
• the reactive gas supply system is mainly composed of the gas supply pipe 232b, the MFC 241b, and the valve 243b.
• the raw material gas supply system and the reactive gas supply system can be collectively referred to as the gas supply system.
• the inert gas supply system is mainly composed of the gas supply pipes 232c, 232d, the MFCs 241c, 241d, and the valves 243c, 243d.
• the inert gas supply system may be considered to be included in the gas supply system.
• the reactive gas supply system can also be referred to as the reducing gas supply system.
• any or all of the various supply systems described above may be configured as an integrated supply system 248 in which the valves 243a to 243d and the MFCs 241a to 241d are integrated.
• the integrated supply system 248 is connected to each of the gas supply pipes 232a to 232d, and the supply operation of various gases into the gas supply pipes 232a to 232d, i.e., the opening and closing operation of the valves 243a to 243d and the flow rate adjustment operation by the MFCs 241a to 241d, are controlled by a controller 121, which will be described later.
• the integrated supply system 248 is configured as an integrated or separate integrated unit, and can be attached and detached to and from the gas supply pipes 232a to 232d, etc., in units of integrated units, and is configured so that maintenance, replacement, expansion, etc. of the integrated supply system 248 can be performed in units of integrated units.
• the reaction tube 203 is provided with an exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201.
• a vacuum pump 246 as a vacuum exhaust device is connected to the exhaust pipe 231 via a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit).
• the APC valve 244 can evacuate and stop the vacuum exhaust in the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is in operation, and further, can adjust the pressure in the processing chamber 201 by adjusting the valve opening based on the 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 be included in the exhaust system.
• a seal cap 219 is provided as a furnace port cover that can airtightly close the lower end opening of the manifold 209.
• the seal cap 219 is made of a metal such as SUS and is formed in a disk shape.
• An O-ring 220b is provided on the upper surface of the seal cap 219 as a sealing member that abuts against the lower end of the manifold 209.
• a rotation mechanism 267 is installed that rotates the boat 217 described below.
• the rotation shaft 255 of the rotation mechanism 267 is connected to the boat 217 through the seal cap 219.
• the rotation mechanism 267 is configured to rotate the wafers 200 by rotating the boat 217.
• the seal cap 219 is configured to be raised and lowered in the vertical direction by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203.
• the boat elevator 115 is configured to be able to load and unload the boat 217 into and out of the processing chamber 201 by lifting and lowering the seal cap 219.
• the boat elevator 115 is configured as a transport device (transport mechanism) that transports the boat 217, i.e., the wafers 200, into and out of the processing chamber 201.
• the boat 217 as a substrate support is configured to support multiple wafers 200, for example 25 to 200, in a horizontal position and aligned vertically with their centers aligned, i.e., arranged at intervals, in multiple stages.
• the boat 217 is made of a heat-resistant material such as quartz or SiC.
• insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages.
• a temperature sensor 263 is installed inside the reaction tube 203 as a temperature detector. By adjusting the power supply to the heater 207 based on the temperature information detected by the temperature sensor 263, the temperature inside the processing chamber 201 is distributed as desired.
• the temperature sensor 263 is configured in an L-shape and is installed along the inner wall of the reaction tube 203.
• the controller 121 which is a control unit (control means), is configured as a computer including a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I/O port 121d.
• the RAM 121b, the storage device 121c, and the I/O port 121d are configured to be able to exchange data with the CPU 121a via an internal bus 121e.
• An input/output device 122 configured as, for example, a touch panel is connected to the controller 121.
• the substrate processing apparatus may be configured to include one control unit or multiple control units. That is, the control for performing the processing sequence described later may be performed using one control unit or multiple control units.
• the multiple control units may be configured as a control system connected to each other by a wired or wireless communication network, and the control for performing the processing sequence described later may be performed by the entire control system.
• control unit when the term “control unit” is used, it may include one control unit, multiple control units, or a control system made up of multiple control units.
• the storage device 121c is composed of, for example, a flash memory, a HDD (Hard Disk Drive), etc.
• a control program for controlling the operation of the substrate processing apparatus 100, a process recipe describing the procedures and conditions of the substrate processing described later, etc. are readably stored in the storage device 121c.
• the process recipe is a combination of procedures in the substrate processing described later that are executed by the controller 121 to obtain a predetermined result, and functions as a program.
• the process recipe and the control program are collectively referred to simply as a program.
• the process recipe is also simply referred to as a recipe.
• the word program is used in this specification, it may include only the recipe alone, only the control program alone, or both.
• the RAM 121b is configured as a memory area (work area) in which the programs and data read by the CPU 121a are temporarily stored.
• the I/O port 121d is connected to the above-mentioned MFCs 241a to 241d, valves 243a to 243d, pressure sensor 245, APC valve 244, vacuum pump 246, heater 207, temperature sensor 263, rotation mechanism 267, boat elevator 115, etc.
• the CPU 121a is configured to read and execute a control program from the storage device 121c, and to read a recipe from the storage device 121c in response to input of an operation command from the input/output device 122, etc.
• the CPU 121a is configured to control the flow rate adjustment of various gases by the MFCs 241a to 241d, the opening and closing of the valves 243a to 243d, the opening and closing of the APC valve 244 and the pressure adjustment operation by the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment operation of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment operation of the boat 217 by the rotation mechanism 267, the raising and lowering operation of the boat 217 by the boat elevator 115, etc.
• the controller 121 can be configured by installing the above-mentioned program stored in an external storage device (for example, a magnetic disk such as a hard disk, an optical disk such as a CD, a magneto-optical disk such as an MO, or a semiconductor memory such as a USB memory) 123 into a computer.
• the storage device 121c and the external storage device 123 are configured as computer-readable recording media on which the program is recorded. Hereinafter, these are collectively referred to as recording media.
• recording media When the term recording media is used in this specification, it may include only the storage device 121c alone, only the external storage device 123 alone, or both.
• the program may be provided to the computer using a communication means such as the Internet or a dedicated line, without using the external storage device 123.
• wafer used in this specification can mean the wafer itself, or a laminate of the wafer and a specified layer or film formed on its surface.
• surface of a wafer used in this specification can mean the surface of the wafer itself, or the surface of a specified layer, etc. formed on the wafer.
• the inside of the processing chamber 201 i.e., the space in which the wafer 200 is present, is evacuated by the vacuum pump 246 so as to reach a desired pressure (vacuum level).
• a desired pressure vacuum level
• the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information (pressure adjustment).
• the vacuum pump 246 is kept in a constantly operating state at least until the processing of the wafer 200 is completed.
• the inside of the processing chamber 201 is heated by the heater 207 so as to reach a desired temperature.
• the amount of electricity supplied to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so as to achieve a desired temperature distribution inside the processing chamber 201 (temperature adjustment).
• the heating inside the processing chamber 201 by the heater 207 is continued at least until the processing of the wafer 200 is completed.
• the raw material gas by using the material described in this disclosure as the raw material gas, it is possible to etch at least a part of the film formed on the wafer 200 or the wafer 200 itself.
• This etching can be caused by the characteristics of the raw material gas itself, by-products generated from the raw material gas, or by-products generated by the reaction between the raw material gas and the reactive gas.
• the raw material gas can also form a film on the wafer 200 by reacting with itself (e.g., decomposition reaction) or by reacting with the raw material gas and the reactive gas.
• the balance between the amount of film formed on the wafer 200 and the amount of etching can be controlled by the supply conditions of the raw material gas and the reactive gas.
• both film formation and etching can occur in the process of supplying the raw material gas and the reactive gas of this disclosure.
• a process in which film formation proceeds with the amount of film formation being predominant in the film formation process, and a process in which etching proceeds with the amount of etching being predominant in the etching process will be described.
• reaction gas supply step S1
• a reactive gas is supplied to the wafer 200 in the processing chamber 201 and exhausted.
• the valve 243b is opened to allow the reactive gas to flow into the gas supply pipe 232b.
• the reactive gas is adjusted in flow rate by the MFC 241b, supplied into the processing chamber 201 through the nozzle 249b, and exhausted from the exhaust pipe 231.
• the valve 243d is opened to allow an inert gas to flow into the gas supply pipe 232d.
• the inert gas is adjusted in flow rate by the MFC 241d, supplied into the processing chamber 201 together with the reactive gas, and exhausted from the exhaust pipe 231.
• the valve 243c is opened to allow the inert gas to flow into the gas supply pipe 232c.
• the inert gas is supplied into the processing chamber 201 through the gas supply pipe 232c and the nozzle 249a, and exhausted from the exhaust pipe 231.
• the main gas flowing in the processing chamber 201 is a reactive gas.
• the reactive gas is supplied to the wafer 200.
• a reducing gas can be used as the reactive gas.
• a gas containing hydrogen element (H) can be used as the reducing gas.
• hydrogen (H 2 ) gas, monosilane (SiH 4 ) gas, disilane (Si 2 H 6 ) gas, trisilane (Si 3 H 8 ) gas, ammonia (NH 3 ) gas, hydrazine (N 2 H 4 ) gas, phosphine (PH 3 ) gas, or the like can be used.
• hydrogen (H 2 ) gas, monosilane (SiH 4 ) gas, disilane (Si 2 H 6 ) gas, trisilane (Si 3 H 8 ) gas, ammonia (NH 3 ) gas, hydrazine (N 2 H 4 ) gas, phosphine (PH 3 ) gas, or the like can be used.
• the reactive gas one or more of these can be used.
• the inert gas for example, in addition to nitrogen ( N2 ) gas, rare gases such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas, etc., can be used. One or more of these can be used as the inert gas.
• step S2 Simultaneous supply of source gas and reactive gas, step S2
• the supply of a raw material gas as a first raw material gas is started while the reactive gas is being supplied to the wafer 200 in the processing chamber 201.
• the valve 243b is open, the valve 243a is opened to allow the raw material gas to flow into the gas supply pipe 232a.
• the raw material gas is adjusted in flow rate by the MFC 241a, supplied into the processing chamber 201 via the nozzle 249a, and exhausted from the exhaust pipe 231.
• the valve 243c is opened to allow an inert gas to flow into the gas supply pipe 232c.
• the inert gas is adjusted in flow rate by the MFC 241c, supplied into the processing chamber 201 together with the raw material gas, and exhausted from the exhaust pipe 231.
• the main gases flowing in the processing chamber 201 at this time are the source gas and the reaction gas.
• the source gas and the reaction gas are supplied to the wafer 200 simultaneously.
• the raw material gas and the reactive gas are supplied so that the partial pressure of the raw material gas is smaller than the partial pressure of the reactive gas. That is, the raw material gas and the reactive gas are supplied so that the supply amount of the raw material gas is smaller than the supply amount of the reactive gas.
• CVD Chemical Vapor Deposition
• the supply amount means one or more of the gas supply parameters, such as the supply time, the supply flow rate, the pressure in the processing chamber 201 at the time of supply, the pressure in the gas supply pipe, the partial pressure of the target gas, the number of supplies, the number of pulses, etc. It may also be two or more parameters, for example, the product of the supply time and the supply flow rate.
• the supply amount can also be referred to as the amount of gas molecules present in the processing chamber 201.
• a gas containing a halogen element can be used as the raw material gas.
• a gas containing a halogen element for example, a gas containing fluorine (F), chlorine (Cl), bromine (Br), iodine (I), etc. can be used.
• the raw material gas one or more of these can be used.
• the source gas a gas containing a halogen element and a metal element can be used.
• the metal element includes transition metals from Group 3 to Group 12, as well as Group 13 elements (e.g., aluminum (Al), gallium (Ga), indium (In)) and silicon element (Si).
• a gas containing a halogen element and a metal element can be used as the raw material gas.
• the metal element includes titanium (Ti), zirconium (Zr), hafnium (Hf) Group 4 elements, Group 13 elements, and elements described in the present disclosure.
• the gas described in the present disclosure titanium tetrachloride (TiCl 4 ) gas, aluminum chloride (AlCl 3 ) gas, hafnium chloride (HfCl 4 ) gas, zirconium chloride (ZrCl 4 ) gas, etc. can be used as the raw material gas.
• a gas containing a halogen element and a transition metal can be used.
• the gas containing a transition metal it is preferable to use a gas containing a Group 6 element such as chromium (Cr), molybdenum (Mo), or tungsten (W).
• a gas containing a Group 6 element such as chromium (Cr), molybdenum (Mo), or tungsten (W).
• a halogen element and a Group 6 element it is possible to use, for example, tungsten hexafluoride (WF 6 ) gas, tungsten hexachloride (WCl 6 ) gas, molybdenum pentachloride (MoCl 5 ) gas, molybdenum dichloride dioxide (MoO 2 Cl 2 ) gas, molybdenum tetrachloride oxide (MoOCl 4 ) gas, molybdenum hexafluoride (MoF 6 ) gas, molybdenum difluoride dioxide (MoO 2 F 2 ) gas, molyb
• a gas containing a halogen element and Si can be used.
• a gas containing a halogen element and Si for example, silicon tetrachloride (SiCl 4 ) gas, dichlorosilane (SiH 2 Cl 2 , abbreviated as DCS) gas, hexachlorodisilane (Si 2 Cl 6 , abbreviated as HCDS) gas, etc. can be used.
• the source gas one or more of these can be used.
• MoCl 5 gas When, for example, MoCl 5 gas is used as the source gas and, for example, H 2 gas is used as the reactive gas, the MoCl 5 gas and the H 2 gas react with each other, so that Cl in the MoCl 5 gas is reduced by the H 2 gas, and a molybdenum (Mo)-containing layer, which is a metal-containing layer, is formed as a first layer on the wafer 200.
• the Mo-containing layer may be a Mo layer containing Cl, an adsorption layer of MoCl 5 , or both.
• reaction gas supply step S3
• the supply of the source gas into the processing chamber 201 is stopped while the supply of the reactive gas is maintained.
• the valve 243a is closed to stop the supply of the source gas into the processing chamber 201.
• the valve 243c is opened to allow an inert gas to flow into the gas supply pipe 232c.
• the inert gas is supplied into the processing chamber 201 via the gas supply pipe 232c and the nozzle 249a, and is exhausted from the exhaust pipe 231.
• the main gas flowing in the processing chamber 201 at this time is reactive gas.
• reactive gas is continuously supplied to the wafer 200 before and after the raw material gas is supplied.
• the supply of the reactive gas is continued without supplying the raw material gas.
• the reaction by-products generated by the supply of the raw material gas and the reactive gas can be removed (purged) from the processing chamber 201, and the reaction by-products remaining in the processing chamber 201 can be prevented from adsorbing onto the wafer 200.
• the unreacted raw material gas can be reacted.
• step S4 By performing a cycle of sequentially performing the above-mentioned steps S1 to S3 a predetermined number of times (n, n is an integer of 1 or 2 or more), a predetermined film of a predetermined thickness is formed on the wafer 200. Specifically, a metal-containing film, such as a Mo-containing film, is formed. If the number of cycles of sequentially performing steps S1 to S3 is less than the predetermined number, the process returns to step S1. Note that although FIG. 4 shows a case where n is 3 or more, n may be 1 or more.
• the supply time of the reactive gas after the supply of the raw material gas has ended is set to be longer than the supply time of the reactive gas before the supply of the raw material gas begins. This can improve the efficiency of removing reaction by-products. Also, the supply time of the reactive gas after the supply of the raw material gas begins is set to be longer than the supply time of the reactive gas before the supply of the raw material gas begins. This can improve the film formation rate by reacting the unreacted raw material gas with the reactive gas.
• a metal-containing film 500 is formed in a recess on a wafer 200, in which a conductive metal-containing film 300 is exposed on the bottom surface and a dielectric film (insulator film) 400 is exposed on the sidewall surface.
• step S1 to S3 When the above-mentioned steps S1 to S3 are repeated a predetermined number of times, selective breaking may occur not only on the metal-containing film 300 in the recess, but also on the dielectric film 400 that forms the sidewall surface of the recess, resulting in the formation of nuclei 500a, as shown in FIG. 5(B).
• nuclei 500a grow, the metal-containing film 500 is not formed uniformly in the recess, and seams and voids may occur in the metal-containing film 500 in the recess, making it impossible to obtain the desired film characteristics.
• an etching step is performed at the timing when the nucleus 500a is formed to remove the nucleus 500a formed on the sidewall surface, etc., of the recess, as shown in FIG. 5(C).
• the main gases flowing in the processing chamber 201 are the source gas and the reaction gas. That is, the source gas and the reaction gas are supplied to the wafer 200 at the same time.
• the same source gas as the source gas in the film formation process of step S2 described above is used.
• the same reaction gas as the reaction gas in the film formation process of step S2 described above is used.
• the partial pressure of the raw material gas is made different from the partial pressure of the raw material gas in step S2 described above.
• the raw material gas and the reactive gas are supplied so that the partial pressure of the raw material gas in this step is larger than the partial pressure of the raw material gas in step S2. That is, the flow rate of the raw material gas in this step is made larger than the flow rate of the raw material gas in step S2. That is, in the etching process, a raw material gas having a different partial pressure from the raw material gas in the film formation process is supplied to the wafer 200, and thus the amount of film formed by the raw material gas and the reactive gas can be made smaller than the amount of etching by the raw material gas and the reactive gas.
• the amount of etching by the raw material gas and the reactive gas can be made larger than the amount of film formed by the raw material gas and the reactive gas, and etching can be made dominant. Therefore, under conditions that make etching dominant in this step, the raw material gas and the reactive gas are supplied, and the nuclei formed on the wafer 200 are removed, and the film is etched. That is, the halogen element contained in the source gas reacts with the reactive gas to generate reaction by-products such as HCl, Cl 2 , and hydrogen fluoride (HF).
• reaction by-products are also called halogen-containing by-products.
• reaction by-products removes the nuclei formed on the wafer 200, making it possible to form a film on the wafer while maintaining selectivity.
• etching by source gas is also considered as an etching mechanism.
• etching by by-products generated by the reaction (e.g., decomposition reaction) of the source gas is also considered. Although there are various mechanisms, the etching can be dominated by the supply amount of the source gas and the conditions that make it easy for the above-mentioned reaction by-products to be generated.
• the supply of the raw material gas and the reactive gas is started and stopped at the same time.
• the supply time of the raw material gas in this step is made shorter than the supply time of the raw material gas in step S2. This makes it possible to remove the nuclei formed in the film formation process.
• the supply time of the raw material gas in this step can be adjusted according to the etching rate.
• a predetermined film of a predetermined thickness is formed in the recess on the wafer 200.
• the predetermined film formed here is a film without seams or voids, and is, for example, a metal-containing film such as a Mo-containing film.
• the number of times (n) in step S4 described above is equal to or greater than the number of times (m) in step S6 described above.
• the number of times (n) is greater than the number of times (m). That is, the number of cycles in the film formation process described above is greater than the number of cycles in the etching process described above, and for example, one cycle in the etching process is performed for every two cycles in the film formation process. This makes it possible to improve the film formation rate while removing nucleus growth, form a uniform film while maintaining selectivity, and improve the properties of the formed film.
• step S4 the above-mentioned steps S1 to S3 are repeated a predetermined number of times (n, where n is an integer of 1 or 2 or more)
• step S5 is performed, whereby the nuclei 500a as shown in FIG. 5(B) are removed as shown in FIG. 5(C).
• step S6 by performing step S6 in which the above-mentioned steps S1 to S5 are repeated a predetermined number of times (m, where m is an integer of 1 or 2 or more), a uniform metal-containing film 500 without seams or voids is formed in the recess on the wafer 200 as shown in FIG. 5(D).
• An inert gas is supplied into the processing chamber 201 from each of the gas supply pipes 232c and 232d, and exhausted from the exhaust pipe 231.
• the inert gas acts as a purge gas. This purges the processing chamber 201, and gas and reaction by-products remaining in the processing chamber 201 are removed from the processing chamber 201 (after-purge). Thereafter, the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas replacement), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure return).
• the seal cap 219 is lowered by the boat elevator 115 to open the lower end of the manifold 209. Then, the processed wafers 200 supported by the boat 217 are unloaded from the lower end of the manifold 209 to the outside of the reaction tube 203 (boat unloading). The processed wafers 200 are removed from the boat 217 (wafer discharging).
• the amount of film formation by the source gas and the reactive gas, and the amount of etching by the source gas and the reactive gas can be adjusted.
• a film can be formed on the wafer 200 so that the amount of film formed by the source gas and the reactive gas is greater than the amount of etching by the source gas and the reactive gas.
• the amount of film formed by the source gas and the reactive gas is made smaller than the amount of etching by the source gas and the reactive gas, so that the film on the wafer 200 can be etched.
• the action of the reaction by-products can remove nuclei formed in the film forming process.
• the film formation rate can be improved by simultaneously supplying the source gas and the reactive gas.
• the reaction by-products generated by the supply of the source gas and the reactive gas can be removed from the processing chamber 201, and the reaction by-products remaining in the processing chamber 201 can be prevented from being adsorbed onto the wafer 200.
• the unreacted source gas can be reacted.
• the supply time of the reactive gas after the supply of the raw material gas is made longer than the supply time of the reactive gas before the supply of the raw material gas. This makes it possible to improve the efficiency of removing reaction by-products while reacting unreacted raw material gas with the reactive gas, thereby improving the film formation rate.
• the raw material gases to be continuously supplied are at least one of the first raw material gas and the second raw material gas.
• FIG. 6 shows a case where n is 3 or more, n may be 1 or more.
• FIGS. 7(A) to 7(F) show modified examples of the film formation process described above
• FIG. 8(A) to 8(F) show modified examples of the etching process described above.
• the source gas and the reaction gas are supplied under conditions such that the amount of film formation is greater than the amount of etching.
• the source gas and the reaction gas are supplied under conditions such that the amount of etching is greater than the amount of film formation.
• the partial pressure of the source gas in the etching process is made greater than the partial pressure of the source gas in the film formation process.
• the number of cycles in the film formation process is made greater than the number of cycles in the etching process, and the supply time of the source gas in the etching process is made shorter than the supply time of the source gas in the film formation process.
• the above-mentioned film formation process or modified example of the film formation process and the above-mentioned etching process or modified example of the etching process can be used in combination.
• Modification 11 In this modification, as shown in Fig. 8D, in one cycle of the etching process, the supply of the source gas and the reactive gas is started simultaneously, and the supply of the source gas is stopped while the reactive gas is being supplied. That is, in one cycle, there is a period during which the supply of the source gas and the supply of the reactive gas overlap. In this modification, the same effects as those of the above embodiment can be obtained.
• Modification 14 In this modification, as shown in Fig. 9, different source gases containing halogen elements are used in the film forming process and the etching process. That is, a first source gas and a second source gas are used as the source gas.
• a first source gas supply system for supplying the first source gas and a second source gas supply system for supplying the second source gas are used.
• the first source gas means the source gas used in the film forming process
• the second source gas means the source gas used in the etching process.
• Fig. 9 shows a case where n is 3 or more, n may be 1 or more.
• a first source gas containing halogen elements and metal elements is used as the source gas.
• a second source gas containing the same halogen elements and metal elements as the first source gas and having a greater number of halogen elements in one molecule than the number of halogen elements in one molecule of the first source gas is used as the source gas.
• the first raw material gas and the reactive gas are supplied simultaneously, and in the above-mentioned step S5, the second raw material gas and the reactive gas are supplied simultaneously.
• the supply of the reactive gas is continued without supplying either the first raw material gas or the second raw material gas.
• the first source gas for example, MoO2Cl2 gas, MoO2F2 gas , WCl3 gas , SiCl4 gas, DCS gas, TiCl4 gas, AlCl3 gas, HfCl4 gas, ZrCl4 gas, etc.
• the first source gas one or more of these can be used.
• the second source gas is a source gas having a larger number of halogen elements contained in one molecule than the first source gas, and for example, MoCl5 gas, WF6 gas, WCl6 gas, MoOCl4 gas , MoOF4 gas , MoF6 gas, HCDS, etc. can be used.
• the same effect as that described above can be obtained. Furthermore, in this modified example, by using a second source gas in the etching process that contains a greater number of halogen elements in one molecule than the first source gas used in the film formation process, the amount of etching in the etching process can be increased, and a stronger etching effect can be obtained.
• a purge step for purging the residual gas in the processing chamber 201 may be provided between the above-mentioned film formation step and the above-mentioned etching step. That is, between the above-mentioned film formation step and the above-mentioned etching step, the supply of the source gas and the reactive gas may be stopped, and purging for removing the atmosphere in the processing chamber 201 may be performed.
• the valves 243a and 243b are closed, and the supply of the source gas and the reactive gas into the processing chamber 201 is stopped. Then, the processing chamber 201 is evacuated to remove the gas remaining in the processing chamber 201 from the processing chamber 201 (purging). At this time, the valves 243c and 243d are opened to supply an inert gas into the processing chamber 201.
• the inert gas acts as a purge gas.
• reaction by-products generated by the supply of the raw material gas and the reactive gas can be removed from the processing chamber 201, and the reaction by-products remaining in the processing chamber 201 can be prevented from being adsorbed onto the wafer 200.
• a cluster-type substrate processing apparatus 10 which has a plurality of processing furnaces 202a to 202d and has a plurality of processing chambers 201a to 201d each connected to a vacuum transfer chamber 103 in which a substrate transfer device 112 is installed, for example.
• the controller 121 performs the above-mentioned film formation process and the above-mentioned etching process separately in different processing chambers of different processing furnaces.
• the wafer 200 is transported under a vacuum atmosphere or an inert gas atmosphere. That is, the substrate processing apparatus 10 performs the film formation process in which a first source gas and a reactive gas are supplied, and the etching process in which a second source gas and a reactive gas are supplied, separately in different processing chambers.
• the same effects as those of the above-mentioned embodiment can be obtained.
• this modified example can be preferably used when the source gas in the film formation process and the source gas in the etching process are different.
• the metal-containing film of the present disclosure is, for example, a film containing at least one of elements of groups 3 to 13 and Si. Preferably, it is a film containing at least one of elements of groups 3 to 13. More preferably, it is a film containing a transition metal.
• the metal-containing film is at least one of a film of a metal element alone having a metal element as the main component, a metal oxide film, a metal nitride film, a metal carbide film, a metal oxynitride film, a metal carbonitride film, and a metal oxycarbide film.
• the metal-containing film 300 of the present disclosure is preferably a metal nitride film.
• the metal-containing film 500 is preferably a film of a metal element alone having a metal element as the main component.
• the metal-containing film 500 is, for example, a metal element alone film having a metal element as the main component including at least one of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Ni, Zn, Al, Ga, In, and Si.
• the metal-containing film 300 may be, for example, a lanthanide nitride film, a TiN film, a ZrN film, a HfN film, a VN film, a NbN film, a TaN film, a MoN film, a WN film, an AlN film, a GaN film, an InN film, etc.
• an example of forming a film using a batch-type substrate processing apparatus that processes multiple substrates at a time has been described.
• the present disclosure is not limited to the above-mentioned embodiment, and can be suitably applied, for example, to a case where a film is formed using a single-wafer 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-mentioned embodiment, and can be suitably applied, for example, to a case where a film is formed using a substrate processing apparatus having a cold-wall type processing furnace.
• the above-mentioned processing sequences may be performed consecutively (in-situ) in the same processing chamber (processing vessel). Also, at least one of the above-mentioned processing sequences and any other processing may be performed in different processing chambers (processing vessels) (ex-situ). In either case, the same effects as the above-mentioned embodiment can be obtained.
• these processings are performed in-situ, contamination of the substrate and changes in the substrate surface condition that may occur when the substrate is removed from the processing chamber between processings or removed from the processing chamber can be suppressed.
• these processings are performed in-situ, the transition time between processings can be shortened.
• the processings can be performed in parallel in different processing chambers, thereby increasing productivity.
• each process can be performed using the same process procedures and conditions as those in the above-mentioned embodiments and modifications, and the same effects as those in the above-mentioned embodiments and modifications can be obtained.

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