Classifications

• • 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
  • C23C16/45536—Use of plasma, radiation or electromagnetic fields
  • C23C16/45538—Plasma being used continuously during the ALD cycle
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
  • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
  • H01J37/32—Gas-filled discharge tubes
  • H01J37/32431—Constructional details of the reactor
  • H01J37/3244—Gas supply means
  • H01J37/32449—Gas control, e.g. control of the gas flow
• • 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
  • C23C16/34—Nitrides
  • C23C16/345—Silicon nitride
• • 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
  • C23C16/45536—Use of plasma, radiation or electromagnetic fields
  • C23C16/45542—Plasma being used non-continuously during the ALD reactions
• • 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
• • 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
  • C23C16/44—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]
  • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
• • 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
  • C23C16/52—Controlling or regulating the coating process
• • 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
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
  • H10P14/6326—Deposition processes
  • H10P14/6328—Deposition from the gas or vapour phase
  • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
  • H10P14/6336—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
  • H10P14/6326—Deposition processes
  • H10P14/6328—Deposition from the gas or vapour phase
  • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
  • H10P14/6339—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/66—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials
  • H10P14/668—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials
  • H10P14/6681—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials the precursor containing a compound comprising Si
  • H10P14/6682—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the type of materials the materials being characterised by the deposition precursor materials the precursor containing a compound comprising Si the compound being a silane, e.g. disilane, methylsilane or chlorosilane
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/69—Inorganic materials
  • H10P14/694—Inorganic materials composed of nitrides
  • H10P14/6943—Inorganic materials composed of nitrides containing silicon
  • H10P14/69433—Inorganic materials composed of nitrides containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz

Definitions

• the present disclosure relates to a substrate processing method, a semiconductor device manufacturing method, a program, and a substrate processing apparatus.
• a process is sometimes performed in which a film is formed on a substrate by alternately supplying a source gas and a reaction gas to the substrate (see, for example, Patent Document 1).
• An object of the present disclosure is to provide a technique for forming a film on a substrate with excellent uniformity of film characteristics within the plane of the substrate.
• FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus suitably used in one embodiment of the present disclosure, and is a diagram showing a portion of the processing furnace in a vertical cross-sectional view.
• FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus preferably used in one embodiment of the present disclosure, and is a cross-sectional view taken along the line AA of the processing furnace portion.
• FIG. 3 is a schematic configuration diagram of a controller of a substrate processing apparatus preferably used in one aspect of the present disclosure, and is a block diagram showing a control system of the controller.
• FIG. 4 is a diagram illustrating an example of main gas supply timing and RF power supply timing in a film formation sequence according to one embodiment of the present disclosure.
• FIG. 5 is a diagram showing an example of a film formation sequence in an example.
• FIG. 6 is a diagram showing measurement results of wet etching rates of films formed in Examples.
• FIG. 7 is a diagram showing the relationship between the wet etching rate and chlorine concentration of the film formed in the example.
• FIGS. 1 to 4. One aspect of the present disclosure will be described below, mainly with reference to FIGS. 1 to 4. Note that the drawings used in the following explanation are all schematic, and the dimensional relationship of each element, the ratio of each element, etc. shown in the drawings do not necessarily match the reality. 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 includes a heater 207 as a heating means (heating mechanism).
• the heater 207 has a cylindrical shape and is vertically installed by being supported by a holding plate.
• the heater 207 also functions as an activation mechanism (thermal excitation unit) that activates (excites) gas with heat.
• a reaction tube 203 is arranged concentrically with the heater 207.
• the reaction tube 203 is made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC), and has a cylindrical shape with a closed upper end and an open lower end.
• a manifold 209 is arranged below the reaction tube 203 and concentrically with the reaction tube 203 .
• the manifold 209 is made of a metal material such as stainless steel (SUS), and has a cylindrical shape with open upper and lower ends. The upper end of the manifold 209 engages with the lower end of the reaction tube 203 and is configured to support the reaction tube 203.
• An O-ring 220a serving as a sealing member is provided between the manifold 209 and the reaction tube 203.
• the reaction tube 203 like the heater 207, is installed vertically.
• the reaction tube 203 and the manifold 209 mainly constitute a processing container (reaction container).
• a processing chamber 201 is formed in the cylindrical hollow part of the processing container.
• the processing chamber 201 is configured to accommodate a wafer 200 as a substrate. Processing of the wafer 200 is performed within this processing chamber 201, that is, within this processing container.
• nozzles 249a to 249c as first to third supply parts are provided so as to penetrate through the side wall of the manifold 209, respectively.
• the nozzles 249a to 249c are also referred to as first to third nozzles, respectively.
• the nozzles 249a to 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 gas supply pipes 232a to 232c are also referred to as first to third gas supply pipes (R1 to R3), respectively.
• the gas supply pipe 232a is provided with an MFC 241a, a valve 243a, and a valve 242a, which are on-off valves, in this order from the upstream side of the gas flow.
• a gas supply pipe 232d is connected to the gas supply pipe 232a downstream of the valve 242a.
• the gas supply pipe 232d is provided with an MFC 241d and a valve 243d, which is an on-off valve, in order from the upstream side of the gas flow.
• the gas supply pipes 232b, 232c are provided with mass flow controllers (MFC) 241b, 241c, which are flow rate controllers (flow rate control units), and valves 243b, 243c, which are on-off valves, in order from the upstream side of the gas flow. .
• MFC mass flow controllers
• a gas supply pipe 232e is connected to the gas supply pipe 232b downstream of the valve 243b.
• Gas supply pipes 232f and 232g are connected to the gas supply pipe 232c downstream of the valve 243c, respectively.
• the gas supply pipes 232e to 232g are provided with MFCs 241e to 241g and valves 243e to 243g, respectively, in order from the upstream side of the gas flow.
• the gas supply pipes 232a to 232g are made of a metal material such as stainless steel (SUS), for example.
• remote plasma units 300b and 300c are provided as excitation units (plasma excitation units, plasma activation mechanisms) that activate (excite) gas with plasma. It is provided.
• the electrodes receive plasma-excited gas inside the remote plasma units 300b, 300c through the gas supply pipes 232b, 232c and the nozzles 249b, 249c by applying electric power, that is, high frequency power (RF power). , can be supplied into the processing chamber 201.
• RF power high frequency power
• a first buffer chamber (buffer structure) accommodating a nozzle 249b and a first plasma generation electrode, which will be described later, is provided inside or outside the reaction tube 203 along the wall surface of the reaction tube 203
• the first buffer chamber and the first plasma generation electrode can also constitute a remote plasma unit that excites the gas supplied from the nozzle 249b to plasma.
• a second buffer chamber accommodating a nozzle 249c and a second plasma generation electrode, which will be described later, is provided inside or outside the reaction tube 203 along the wall surface of the reaction tube 203.
• the buffer chamber and the second plasma generation electrode can also constitute a remote plasma unit that excites the gas supplied from the nozzle 249c to plasma.
• the first buffer chamber, the second buffer chamber, the first plasma generation electrode, and the second plasma generation electrode may be configured as a common buffer chamber and plasma generation electrode, respectively. .
• 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 each provided so as to rise upward in the direction in which the wafers 200 are arranged. That is, the nozzles 249a to 249c are respectively provided along the wafer array region in a region horizontally surrounding the wafer array region on the side of the wafer array region where the wafers 200 are arrayed.
• the nozzle 249a is located farther from the exhaust port 231a, which will be described later, than the nozzles 249b and 249c. That is, the nozzles 249b and 249c are arranged closer to the exhaust port 231a than the nozzle 249a. Further, the nozzles 249b and 249c have an axis of symmetry with respect to a straight line passing through the center of the wafer 200 when the wafer 200 is carried into the processing chamber 201, that is, the center of the reaction tube 203 and the center of the exhaust port 231a, in a plan view. are arranged line-symmetrically. Further, the nozzles 249a and 249b are arranged to face each other in a straight line with the center of the reaction tube 203 in between.
• 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 opens toward the center of the reaction tube 203, making it possible to supply gas toward the wafer 200.
• the gas supply holes 250a and 250b are open so as to face each other in a straight line across the center of the wafer 200, that is, the center of the reaction tube 203.
• a plurality of gas supply holes 250a to 250c are provided from the bottom to the top of the reaction tube 203.
• a gas containing a predetermined element and a halogen element is supplied as a raw material gas into the processing chamber 201 via the MFC 241a, the valve 243a, the valve 242a, and the nozzle 249a.
• a gas composed of one type of element is supplied into the processing chamber 201 through the MFC 241b, the valve 243b, and the nozzle 249b.
• a gas containing nitrogen (N) as a reaction gas is supplied from the gas supply pipe 232c into the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c.
• a gas composed of multiple types of elements is supplied into the processing chamber 201 as a compound gas via the MFC 241f, the valve 243f, the gas supply pipe 232c, and the nozzle 249c.
• the simple gas and the compound gas are supplied from the respective nozzles 249b and 249c, the respective gases may be supplied from the same nozzle.
• the simple gas and the reaction gas are supplied from the respective nozzles 249b and 249c, the respective gases may be supplied from the same nozzle.
• the simple gas, the reaction gas, and the compound gas may be supplied from one nozzle (for example, one of the nozzles 249b and 249c).
• Inert gas is supplied from the gas supply pipes 232d, 232e, and 232g into the processing chamber 201 via MFCs 241d, 241e, and 241g, valves 243d, 243e, and 243g, gas supply pipes 232a to 232c, and nozzles 249a to 249c, respectively. be done.
• the inert gas acts as a purge gas, carrier gas, diluent gas, etc.
• a raw material gas supply system is mainly composed of the gas supply pipe 232a, MFC 241a, valves 243a, 242a, and gas reservoir.
• a reaction gas supply system is mainly composed of the gas supply pipe 232b, MFC 241b, and valve 243b.
• a single gas supply system is mainly composed of the gas supply pipe 232c, MFC 241c, and valve 243c.
• a compound gas supply system is mainly composed of the gas supply pipe 232f, the MFC 241f, and the valve 243f.
• An inert gas supply system is mainly composed of gas supply pipes 232d, 232e, 232g, MFCs 241d, 241e, 241g, and valves 243d, 243e, 243g.
• any or all of the various gas supply systems described above are configured as an integrated gas supply system 248 in which valves 243a to 243g, gas reservoirs, MFCs 241a to 241g, etc. are integrated. Good too.
• the integrated gas supply system 248 is connected to each of the gas supply pipes 232a to 232g, and performs operations for supplying various gases into the gas supply pipes 232a to 232g, that is, opening and closing operations of valves 243a to 243g, and MFCs 241a to 241g.
• the flow rate adjustment operation and the like are controlled by a controller 121, which will be described later.
• the integrated gas supply system 248 is configured as an integral type or a split type integrated unit, and can be attached to and detached from the gas supply pipes 232a to 232f, etc. in units of integrated units.
• the structure is such that maintenance, replacement, expansion, etc. of the H.248 can be performed on an integrated unit basis.
• An exhaust port 231a is provided below the side wall of the reaction tube 203 to exhaust the atmosphere inside the processing chamber 201.
• the exhaust port 231a may be provided along the upper part than the lower part of the side wall of the reaction tube 203, that is, along the wafer arrangement region.
• An exhaust pipe 231 is connected to the exhaust port 231a.
• the exhaust pipe 231 is connected to a pressure sensor 245 as a pressure detector (pressure detection unit) that detects the pressure inside the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit).
• a vacuum pump 246 as a vacuum evacuation device is connected.
• the APC valve 244 can perform evacuation and stop of evacuation in the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating, and further, with the vacuum pump 246 operating,
• the pressure inside the processing chamber 201 can be adjusted by adjusting the valve opening based on pressure information detected by the pressure sensor 245.
• An exhaust system is mainly composed of an exhaust pipe 231, an APC valve 244, and a pressure sensor 245.
• the vacuum pump 246 may be included in the exhaust system.
• a seal cap 219 is provided below the manifold 209 as a furnace mouth cover that can airtightly close the lower end opening of the manifold 209.
• the seal cap 219 is made of a metal material such as SUS, and has a disk shape.
• An O-ring 220b serving as a sealing member that comes into contact with the lower end of the manifold 209 is provided on the upper surface of the seal cap 219.
• a rotation mechanism 267 for rotating the boat 217, which will be described later, is installed below the seal cap 219.
• the rotation shaft 255 of the rotation mechanism 267 is made of a metal material such as SUS, and is connected to the boat 217 through the seal cap 219 .
• the rotation mechanism 267 is configured to rotate the wafer 200 by rotating the boat 217.
• the seal cap 219 is configured to be vertically raised and lowered by a boat elevator 115 serving as a raising and lowering mechanism installed outside the reaction tube 203.
• the boat elevator 115 is configured as a transport device (transport mechanism) that transports the wafer 200 into and out of the processing chamber 201 by raising and lowering the seal cap 219 .
• a shutter 219s is provided below the manifold 209 as a furnace mouth cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is taken out of the processing chamber 201.
• the shutter 219s is made of a metal material such as SUS, and has a disk shape.
• An O-ring 220c as a sealing member that comes into contact with the lower end of the manifold 209 is provided on the upper surface of the shutter 219s.
• the opening and closing operations (elevating and lowering operations, rotating operations, etc.) of the shutter 219s are controlled by a shutter opening and closing mechanism 115s.
• the boat 217 which serves as a support for the substrates, supports a plurality of wafers 200, for example, 25 to 200 wafers 200, in a horizontal position and aligned vertically with their centers aligned with each other in multiple stages. It is configured. That is, the boat 217 is configured to arrange a plurality of wafers 200 horizontally and at intervals in the vertical direction.
• the boat 217 is made of a heat-resistant material such as quartz or SiC.
• heat insulating plates 218 made of a heat-resistant material such as quartz or SiC are supported in multiple stages.
• the boat 217 is configured to be able to support a plurality of wafers 200, respectively.
• a temperature sensor 263 as a temperature detector is installed inside the reaction tube 203. 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 becomes a desired temperature distribution. Temperature sensor 263 is provided along the inner wall of reaction tube 203.
• the controller 121 which is a control unit (control means), is configured as a computer equipped with a CPU (Central Processing Unit) 121a, a RAM (Random Access Memory) 121b, a storage device 121c, and an I/O port 121d. has been done.
• the RAM 121b, storage device 121c, and 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 .
• an external storage device 123 can be connected to the controller 121.
• the storage device 121c is configured with, for example, a flash memory, an HDD (Hard Disk Drive), an SSD (Solid State Drive), or the like.
• a control program for controlling the operation of the film forming apparatus, a process recipe in which processing procedures, conditions, etc. to be described later are described, and the like are stored in a readable manner.
• a process recipe is a combination of steps such that the controller 121 causes the film forming apparatus to execute each procedure in a process described later to obtain a predetermined result, and functions as a program.
• process recipes, control programs, etc. will be collectively referred to as simply programs.
• a process recipe is also simply referred to as a recipe.
• the word program When the word program is used in this specification, it may include only a single recipe, only a single control program, or both.
• the RAM 121b is configured as a memory area (work area) in which programs, data, etc. read by the CPU 121a are temporarily held.
• the I/O port 121d includes the above-mentioned MFCs 241a to 241g, valves 243a to 243g, pressure sensor 245, APC valve 244, vacuum pump 246, temperature sensor 263, heater 207, rotation mechanism 267, boat elevator 115, shutter opening/closing mechanism 115s, etc. 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.
• the CPU 121a adjusts the flow rate of various gases by the MFCs 241a to 241g, opens and closes the valves 243a to 243g, opens and closes the APC valve 244, and adjusts the pressure by the APC valve 244 based on the pressure sensor 245 in accordance with the contents of the read recipe.
• the controller 121 can be configured by installing the above-mentioned program stored in the external storage device 123 into a 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 will be collectively referred to as simply recording media.
• recording medium may include only the storage device 121c, only the external storage device 123, or both.
• 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.
• Substrate processing process A substrate processing sequence in which a film containing a predetermined element and nitrogen (N) is formed on a wafer 200 as a substrate using the above-described substrate processing apparatus as a step in the manufacturing process of a semiconductor device. , an example of a film formation sequence will be explained. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by a controller 121.
• the ratio of the compound gas supply flow rate to the simple gas supply flow rate is set to less than 1/2, thereby reducing the compound gas supply rate to the simple gas supply rate.
• An example in which the ratio is less than 1/2 is shown.
• the ratio of the supply amount of the compound gas to the supply amount of the simple gas is preferably 1/3 or less.
• the film containing a predetermined element and N includes not only a nitride film (SiN film) containing a predetermined element such as silicon but also a nitride film containing carbon (C) and oxygen (O).
• the nitride film includes a silicon nitride film (SiN film), a silicon carbonitride film (SiCN film), a silicon oxynitride film (SiON film), a silicon oxycarbonitride film (SiOCN film), and the like.
• a predetermined element is Si and a SiN film is formed as a film containing Si and N.
• the word “wafer” may mean the wafer itself, or it may mean a stack of a wafer and a predetermined layer or film formed on its surface.
• the term “wafer surface” when used, it may mean the surface of the wafer itself, or the surface of a predetermined layer formed on the wafer.
• the expression “forming a predetermined layer on a wafer” may mean forming a predetermined layer directly on the surface of the wafer itself, or may mean forming a predetermined layer directly on the surface of the wafer itself, or may mean forming a predetermined layer directly on the surface of the wafer. It may mean forming a predetermined layer on top.
• substrate when the word "substrate” is used, it has the same meaning as when the word "wafer” is used.
• the inside of the processing chamber 201 is evacuated (decompressed) by the vacuum pump 246 so that the desired pressure (degree of vacuum) is achieved.
• the pressure inside the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled (pressure adjustment) based on the measured pressure information.
• the wafer 200 in the processing chamber 201 is heated by the heater 207 so as to reach a desired processing temperature.
• the energization 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).
• rotation of the wafer 200 by the rotation mechanism 267 is started. The operation of the vacuum pump 246 and the heating and rotation of the wafer 200 are all continued at least until the processing on the wafer 200 is completed.
• the valve 242a is closed, the valve 243a is opened, and the source gas flows into the gas supply pipe 232a.
• the flow rate of the source gas is adjusted by the MFC 241a, and is stored in the gas supply pipe 232a (hereinafter also referred to as a gas reservoir) between the valves 243a and 242a.
• the gas reservoir is filled with the raw material gas.
• the valve 243a is closed to maintain the state in which the gas reservoir is filled with the raw material gas.
• step A source gas is supplied to the wafer 200 in the processing chamber 201 .
• valve 242a is opened, and the high-pressure raw material gas filled in the gas reservoir is supplied into the processing chamber 201 at once (pulse-like) via the gas supply pipe 232a and the nozzle 249a.
• this supply method will be referred to as flash flow.
• the valves 243d, 243e, and 243g are opened to supply inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively. Note that in some of the methods described below, the supply of inert gas may not be implemented. Further, it is preferable that this step is carried out with the exhaust system substantially fully closed (APC valve 244 substantially fully closed).
• the pressure within the processing chamber 201 rapidly increases to a predetermined pressure. Thereafter, the pressurized state in the processing chamber 201 is maintained for a predetermined period of time, and the wafer 200 is exposed to a high-pressure source gas atmosphere.
• the processing conditions in this step are: Processing temperature: 250-600°C, preferably 300-600°C Processing pressure (before flash flow): 30-600Pa Processing pressure (after flash flow): 500-1500Pa Raw material gas supply amount (R1): 120 to 360 cc, preferably 120 to 240 cc Raw material gas exposure time: 1 to 20 seconds, preferably 5 to 10 seconds Inert gas supply flow rate (for each R1 to 3): 0 to 10 slm, preferably 0 to 5 slm is exemplified.
• the processing temperature means the temperature of the wafer 200 or the temperature inside the processing chamber 201
• the processing pressure means the pressure inside the processing chamber 201.
• gas supply flow rate: 0slm means a case where the gas is not supplied. The same applies to the following description.
• a Si-containing layer containing Cl is formed as a first layer on the outermost surface of the wafer 200 as a base. be done.
• the Si-containing layer containing Cl causes physical adsorption or chemical adsorption of molecules of chlorosilane gas to the outermost surface of the wafer 200, physical adsorption or chemical adsorption of molecules of a substance partially decomposed of chlorosilane gas, or physical adsorption or chemical adsorption of molecules of a substance that is partially decomposed of chlorosilane gas. It is formed by the deposition of Si due to the thermal decomposition of.
• the Si-containing layer containing Cl may be an adsorption layer (physical adsorption layer or chemical adsorption layer) of molecules of chlorosilane-based gas or molecules of a substance partially decomposed of chlorosilane-based gas, and may be an adsorption layer (physical adsorption layer or chemical adsorption layer) of molecules of chlorosilane-based gas or molecules of a substance in which a part of chlorosilane-based gas is decomposed. It may be a layer.
• the Si-containing layer containing Cl is also simply referred to as the Si-containing layer.
• the processing temperature is less than 250° C.
• Si may be difficult to adsorb onto the wafer 200, making it difficult to form the first layer.
• the processing temperature is set to 250° C. or higher, it becomes possible to form the first layer on the wafer 200.
• the processing temperature By setting the processing temperature to 300° C. or higher, it becomes possible to more fully form the first layer on the wafer 200.
• the raw material gas such as a chlorosilane gas
• Si is deposited in multiple layers on the wafer 200, resulting in a substantially uniform thickness of less than one atomic layer. It may be difficult to form the first layer.
• the processing temperature is set to 600° C. or less, it is possible to form a first layer having a substantially uniform thickness of less than one atomic layer, and it is possible to improve the uniformity of the film thickness within the wafer surface.
• a layer with a thickness of less than one atomic layer means an atomic layer formed discontinuously
• a layer with a thickness of one atomic layer means an atomic layer formed continuously. It means.
• the fact that the layer having a thickness of less than one atomic layer is substantially uniform means that atoms are adsorbed on the surface of the wafer 200 at a substantially uniform density.
• a first layer containing Cl can be formed on the wafer 200, and further, the outer periphery of the wafer 200 can be
• the Cl concentration in the first layer formed in the central part of the wafer 200 can be the same as the Cl concentration in the first layer formed in the central part of the wafer 200.
• the term "same Cl concentration" is used to mean that the Cl concentrations not only match completely, but also include a predetermined error range.
• the predetermined error range is, for example, a ratio of Cl concentration (outer periphery)/(center) between 0.80 and 1.20 between the outer periphery and the center of the wafer 200.
• the valve 242a is closed and the supply of source gas into the processing chamber 201 is stopped. Then, the APC valve 244 is fully opened, for example, to evacuate the inside of the processing chamber 201, and gas and the like remaining in the processing chamber 201 are removed from the inside of the processing chamber 201 (purge). At this time, the valves 243d, 243e, and 243g are kept open to maintain the supply of inert gas into the processing chamber 201.
• the inert gas supplied through each of the nozzles 249a to 249c acts as a purge gas, thereby purging the inside of the processing chamber 201 (purge).
• the processing conditions for purge are as follows: Processing temperature: 250-600°C, preferably 300-600°C Processing pressure: 1 to 70 Pa, preferably 1 to 30 Pa Inert gas supply flow rate (for each R1 to 3): 0.05 to 20 slm, preferably 1 to 5 slm Inert gas supply time: 1 to 20 seconds, preferably 1 to 10 seconds.
• a silane-based gas containing silicon (Si) as the main element constituting the film formed on the wafer 200 can be used.
• silane gas for example, a gas containing halogen and Si, that is, a halosilane gas can be used.
• Halogens include chlorine (Cl), fluorine (F), bromine (Br), iodine (I), and the like.
• halosilane gas for example, the above-mentioned chlorosilane gas containing Cl and Si can be used.
• Examples of the raw material gas include dichlorosilane (SiH 2 Cl 2 , abbreviation: DCS) gas, monochlorosilane (SiH 3 Cl, abbreviation: MCS) gas, trichlorosilane (SiHCl 3 , abbreviation: TCS) gas, and tetrachlorosilane (SiCl 3 , abbreviation: TCS) gas.
• Chlorosilane-based gases such as 4CS , hexachlorodisilane gas (Si 2 Cl 6 , HCDS), and octachlorotrisilane (Si 3 Cl 8 , OCTS) gas can be used.
• the raw material gas one or more of these can be used.
• the inert gas for example, a rare gas such as nitrogen (N 2 ) gas, argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas can be used.
• a rare gas such as nitrogen (N 2 ) gas, argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas
• nitrogen (N 2 ) gas argon (Ar) gas
• He helium
• Ne neon
• xenon (Xe) gas xenon
• Step B After step A is completed, a single gas and a compound gas are each excited in plasma and supplied to the wafer 200 in the processing chamber 201, that is, the first layer (Si-containing layer) formed on the wafer 200. .
• the valves 243b and 243f are opened to flow the simple gas and compound gas into the gas supply pipes 232b and 232c, respectively. .
• the flow rates of the simple gas and the compound gas are adjusted by the MFCs 241b and 241f, respectively, and are supplied into the processing chamber 201 through the nozzles 249b and 249c, and are exhausted from the exhaust port 231a.
• a simple gas or a compound gas is supplied to the wafer 200 from the side of the wafer 200 (that is, from the outer edge of the wafer 200 in the in-plane direction) (single gas or compound gas supply).
• the valves 243d, 243e, and 243g are kept open to maintain the supply of inert gas into the processing chamber 201.
• the simple gases and compound gases supplied into the gas supply pipes 232b and 232c are excited into plasma in the remote plasma units 300b and 300c, respectively.
• Active species X and compound gases produce active species X and Z, respectively, from the simple gas.
• the single gas and compound gas containing the active species X and the active species Z generated in this way are supplied to the wafer 200 (plasma-excited single gas/compound gas supply).
• H 2 gas when hydrogen (H 2 ) gas is used as a single gas composed of one type of element, the H 2 gas is plasma-excited, active species X such as H 2 * are generated, and the wafer 200 is Supplied.
• H 2 * means a radical.
• the hydrogen nitride gas is plasma-excited to generate active substances such as NH 3 * .
• a seed Z is generated and supplied to the wafer 200.
• the processing conditions in this step are: Processing temperature: 250-600°C, preferably 300-600°C Processing pressure: 1 to 100 Pa, preferably 1 to 50 Pa Single gas supply flow rate: 0.1 to 3.0 slm, preferably 0.2 to 1.0 slm Single gas supply time: 5 to 60 seconds, preferably 5 to 20 seconds Compound gas supply flow rate: 0.05 to 1.0 slm, preferably 0.1 to 0.5 slm Compound gas supply time: 5 to 60 seconds, preferably 5 to 20 seconds Inert gas supply flow rate (for each R1 to 3): 0 to 10 slm, preferably 0 to 1.5 slm High frequency power (RF power): 50-1000W, preferably 50-300W is exemplified.
• RF power radio frequency power
• a halogen element is removed from the first layer (Si-containing layer) formed on the surface of the wafer 200 in step A.
• the first layer is modified so that Cl is eliminated. Further, a portion of the first layer is modified, for example, to be nitrided. In this way, a layer that is a modified first layer (hereinafter referred to as a modified layer) is formed on the surface of the wafer 200. This will be explained in detail below.
• Cl can be desorbed from the first layer formed on the wafer 200.
• the active species X supplied into the processing chamber 201 flows from the outer periphery of the wafer 200 toward the center.
• the active species X for example, H 2 *
• the degree of Cl desorption at the center of the wafer 200 is weaker than the degree of Cl desorption at the outer periphery of the wafer 200, and the Cl concentration at the center of the wafer 200 is lower than the Cl concentration at the outer periphery.
• the plasma-excited compound gas is supplied in an amount (in this embodiment, the supply flow rate) that is less than 1/2 of the supply amount (in this embodiment, the supply flow rate) of the plasma-excited single gas.
• the wafer 200 is fed from the side.
• the active species Z supplied into the processing chamber 201 under such conditions flows from the outer periphery of the wafer 200 toward the center. Since the amount of compound gas supplied in this step is small compared to the amount of single gas supplied, active species Z (e.g. NH 3 * ) supplied into the processing chamber 201 are formed on the outer circumference of the wafer 200, for example. It combines with Si on the first layer and is consumed, and almost never reaches the center.
• the degree of inhibition of Cl desorption at the outer peripheral portion of the wafer 200 can be made stronger than the degree of inhibition of Cl desorption at the central portion. Therefore, the degree of Cl desorption at the outer periphery of the wafer 200 by the active species X can be made comparable to the degree of Cl desorption at the center, and the Cl concentration at the outer periphery can be changed It becomes possible to maintain the same Cl concentration as .
• the term "same Cl concentration” is used to mean that the Cl concentrations not only match completely, but also include a predetermined error range.
• the predetermined error range is, for example, a ratio of Cl concentration (outer periphery)/(center) between 0.80 and 1.20 between the outer periphery and the center of the wafer 200.
• the reason why the desorption of Cl from the first layer can be inhibited by supplying the active species Z to the wafer 200 is because the active species Z having a three-dimensional structure is present on the surface of the wafer 200. It is thought that this is because the adsorption of the active species X and the adsorption of the polar active species Z prevent the active species X from reaching the first layer.
• the ratio of the supply amount of plasma-excited compound gas to the supply amount of plasma-excited simple gas becomes 1/2 or more
• the amount of the supplied active species Z that produces the effect of inhibiting the desorption of Cl The above amount may reach the center of the wafer 200, and desorption of Cl may be inhibited over almost the entire surface of the first layer. That is, when the ratio of the supply amount of the plasma-excited compound gas to the supply amount of the plasma-excited simple gas becomes 1/2 or more, the Cl desorption effect obtained by supplying the active species This may be suppressed over the entire plane, and the effect of desorption of Cl by the active species X may not be sufficiently obtained.
• the ratio of the supply amount of the plasma-excited compound gas to the supply amount of the plasma-excited simple gas is less than 1/2, the arrival of the active species Z to the center of the wafer 200 is restricted, and the While maintaining the Cl desorption effect by the active species X, the effect of suppressing Cl desorption by the active species Z in the outer peripheral portion can be obtained.
• the treatment temperature is less than 250°C, the Cl elimination reaction by the active species X may become difficult to occur.
• the treatment temperature By setting the treatment temperature to 250° C. or higher, it becomes possible to promote the Cl elimination reaction by the active species X.
• the treatment temperature By setting the treatment temperature to 300° C. or higher, the Cl elimination reaction by the active species X can proceed more reliably.
• the treatment temperature exceeds 600°C, the reaction of inhibiting Cl desorption by the active species Z may become difficult to occur.
• the treatment temperature By setting the treatment temperature to 600° C. or lower, it becomes possible to promote the Cl desorption inhibition reaction by the active species Z.
• valves 243b and 243f are closed, the application of RF power to the plasma generation electrode is stopped, and the supply of the simple gas and compound gas to the processing chamber 201 is stopped. do. At this time, the valves 243d, 243e, and 243g are kept open to maintain the supply of inert gas into the processing chamber 201.
• the simple gas in addition to the above-mentioned H 2 gas, for example, nitrogen (N 2 ) gas, rare gas such as argon (Ar) gas, helium (He) gas, or at least one of these gases may be used. I can do it.
• nitrogen (N 2 ) gas for example, nitrogen (N 2 ) gas, rare gas such as argon (Ar) gas, helium (He) gas, or at least one of these gases may be used. I can do it.
• N 2 gas is plasma-excited and active species X such as N * and N 2 * are generated.
• Ar gas is plasma-excited and active species X such as Ar * are generated.
• He gas is used as the simple gas, for example, the He gas is plasma excited and active species X such as He * are generated.
• hydrogen nitride gas such as ammonia (NH 3 ) gas, diazene (N 2 H 2 ) gas, hydrazine (N 2 H 4 ) gas, N 3 H 8 gas, etc. can be used.
• NH 3 ammonia
• N 2 H 2 diazene
• N 2 H 4 hydrazine
• N 3 H 8 gas N 3 H 8 gas
• the hydrogen nitride-based gas is plasma-excited and active species Z such as NH * , NH 2 * , NH 3 * , etc. are generated.
• Step C After step B is completed, a reactive gas is plasma-excited and supplied to the wafer 200 in the processing chamber 201, that is, the modified layer formed on the wafer 200. Note that in this embodiment, the inside of the processing chamber 201 is not purged between Step B and Step C.
• the valve 243c is opened to flow the reaction gas into the gas supply pipe 232c.
• the reaction gases are each adjusted in flow rate by the MFC 241c, supplied into the processing chamber 201 via the nozzle 249c, and exhausted from the exhaust port 231a.
• a reactive gas is supplied to the wafer 200 from the side of the wafer 200 (reactive gas supply).
• the valves 243d, 243e, and 243g are kept open to maintain the supply of inert gas into the processing chamber 201.
• the reactive gas supplied into the gas supply pipe 232c is excited into plasma within the remote plasma unit 300c, and active species Y are generated.
• the reaction gas containing the active species Y thus generated is supplied to the wafer 200 (plasma-excited reaction gas supply).
• the hydrogen nitride gas is plasma-excited and active species Y such as NH * , NH 2 * , NH 3 * , etc. generated and supplied to the wafer 200.
• the processing conditions in this step are: Processing temperature: 250-600°C, preferably 300-600°C Processing pressure: 1 to 100 Pa, preferably 1 to 50 Pa Reaction gas supply flow rate: 0.1 to 10 slm, preferably 0.5 to 5.0 slm Reaction gas supply time: 1 to 60 seconds, preferably 10 to 40 seconds Inert gas supply flow rate (for each R1 to 3): 0 to 10 slm, preferably 0 to 1.5 slm High frequency power (RF power): 50-1000W, preferably 50-300W is exemplified.
• a silicon nitride layer (SiN layer), which is a layer containing Si and N, is formed as a second layer on the surface of the wafer 200.
• impurities such as Cl contained in the modified layer constitute a gaseous substance containing at least Cl in the process of the reforming reaction using the plasma-excited reaction gas, and Expelled from within.
• the second layer becomes a layer containing less impurities such as Cl than the modified layer formed in step B.
• the processing temperature is less than 250°C
• the reaction gas becomes difficult to thermally decompose, and it may become difficult to form the second layer.
• the processing temperature By setting the processing temperature to 250° C. or higher, it becomes possible to form the second layer.
• the processing temperature By setting the processing temperature to 300° C. or higher, it becomes possible to form the second layer reliably.
• the processing temperature exceeds 600°C
• the thermal decomposition of the reaction gas becomes excessive, which may make it difficult to form the second layer.
• the processing temperature is set to 600° C. or lower, it becomes possible to suppress excessive thermal decomposition of the reaction gas and form the second layer.
• the valve 243c is closed, the application of RF power to the electrode for plasma generation is stopped, and the supply of reaction gas into the processing chamber 201 is stopped. Then, gas remaining in the processing chamber 201 is removed from the processing chamber 201 using the same processing procedure and processing conditions as in the purge in step A.
• reaction gas for example, hydrogen nitride gas such as NH 3 gas, N 2 H 2 gas, N 2 H 4 gas, N 3 H 8 gas, etc. can be used. One or more of these can be used as the reaction gas.
• a gas containing N, C, and H can also be used as the reaction gas.
• the N, C and H containing gas for example, amine gas or organic hydrazine gas can be used.
• the N, C, and H-containing gas is also an N-containing gas, a C-containing gas, an H-containing gas, and a N- and C-containing gas.
• reaction gas examples 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 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, organic hydrazine gas such as trimethylhydrazine ((CH 3 ) 2 N 2 (CH 3 )H, abbreviation
• a SiN film is formed on the surface of the wafer 200 by performing the above-mentioned steps A, B, and C non-simultaneously, that is, without synchronization, a predetermined number of times (n times, n is an integer of 1 or more). I can do it.
• the above-described cycle is repeated multiple times. That is, the thickness of the SiN layer formed per cycle is made thinner than the desired thickness, and the above-mentioned cycles are repeated until the thickness of the film formed by stacking the SiN layers reaches the desired thickness. It is preferable to repeat this multiple times.
• step B described above by desorbing Cl from the first layer, the wet etching rate (WER) of the SiN film formed by repeating the above cycle can be reduced.
• step B described above by making the Cl concentration at the outer periphery of the wafer 200 (substantially) the same as the Cl concentration at the center of the wafer 200, the center of the SiN film formed by repeating the above cycle is
• the WER at the outer circumferential portion and the outer peripheral portion can be made to be substantially the same. This makes it possible to improve the uniformity of wet etching of the SiN film within the wafer surface (hereinafter also simply referred to as in-plane uniformity). That is, it is possible to make the film characteristics of the central portion and the outer peripheral portion of the SiN film substantially the same, thereby improving the in-plane uniformity of the film characteristics of the SiN film.
• an inert gas is supplied as a purge gas into the process chamber 201 from each of the nozzles 249a to 249c, and is exhausted from the exhaust port 231a.
• the inside of the processing chamber 201 is purged, and gases, reaction byproducts, etc. remaining in the processing chamber 201 are removed from the inside of the processing chamber 201 (after purge).
• the atmosphere inside the processing chamber 201 is replaced with an inert gas (inert gas replacement), and the pressure inside the processing chamber 201 is returned to normal pressure (atmospheric pressure return).
• step B by supplying a simple gas, active species X can desorb Cl from the first layer. This makes it possible to densify the first layer and make the film finally formed on the wafer 200 a film with low WER. Further, in step B, by supplying the compound gas, the desorption of Cl from the first layer is inhibited by the active species Z, and the distribution of the degree of desorption of Cl by the active species X within the plane of the wafer 200 is can be controlled.
• step B by setting the ratio of the supply amount of the compound gas to the supply amount of the simple gas to be less than 1/2, the degree of desorption of Cl at the outer circumference of the wafer 200 is lower than that at the center of the wafer 200.
• the degree of inhibition (of Cl desorption) at the outer periphery of the wafer 200 stronger than the degree of inhibition (of Cl desorption) at the center of the wafer 200 under a situation where the degree of Cl desorption is stronger than the degree of Cl desorption. Can be done.
• the Cl concentration in the first layer at the outer peripheral portion of the wafer 200 after step B can be made the same as the Cl concentration in the first layer at the central portion of the wafer 200.
• step B by setting the ratio of the supply amount of compound gas to the supply amount of simple gas to 1/3 or less, a film with low WER and excellent in-plane uniformity of WER can be reliably produced. It becomes possible to form. If the ratio of the supply amount of the compound gas to the supply amount of the simple gas is more than 1/3, the Cl concentration particularly in the central part of the wafer 200 cannot be sufficiently reduced, and the desired in-plane uniformity of WER may not be achieved. You may not be able to obtain it.
• step B by setting the ratio of the supply amount of the compound gas to the supply amount of the simple gas to be less than 1/2, the processing temperature in steps A to C is kept at a relatively low temperature of 250 to 600°C. Also, it is possible to form a film with low WER and excellent in-plane uniformity of WER. By making the processing temperature in steps A to C relatively low, damage to the processing furnace 202 and wafer 200 can be reduced.
• step B both the simple gas and the compound gas are supplied from the side of the wafer 200 by setting the ratio of the supply amount of the compound gas to the supply amount of the simple gas to be less than 1/2. Even when processing is performed using a so-called vertical processing furnace, it is possible to form a film with low WER and excellent in-plane uniformity of WER. Since a batch-type vertical processing furnace that processes a plurality of wafers 200 at once can be used, the productivity of film-forming processing can be improved.
• the present disclosure is not limited thereto.
• the present disclosure describes titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), niobium (Nb), molybdenum (Mo), tungsten (W), yttrium (Y), strontium (Sr). It is also suitably applicable to the case of forming a nitride film (metal nitride film) containing a metal element such as lanthanum (La), ruthenium (Ru), or aluminum (Al) as a main element.
• a metal element such as lanthanum (La), ruthenium (Ru), or aluminum (Al)
• titanium tetrachloride (TiCl 4 ) gas, hafnium tetrachloride (HfCl 4 ) gas, tantalum pentachloride (TaCl 5 ) gas, trimethylaluminum (Al(CH 3 ) 3 , abbreviation: TMA) gas, etc. are used as the raw material gas.
• Metal nitride film such as titanium nitride film (TiN film), hafnium nitride film (HfN film), tantalum nitride film (TaN film), aluminum nitride film (AlN film), etc.
• the present disclosure is also suitably applicable to the case of forming a film.
• the processing procedure and processing conditions of the film forming process at this time can be the same as those of the above-mentioned embodiment and modification. Even in these cases, the same effects as the above-described embodiments and modifications can be obtained. That is, the present disclosure is suitably applied when forming a semimetal nitride film containing a semimetal element such as Si as a main element, or when forming a metal nitride film containing the above-mentioned various metal elements as a main element. be able to.
• the ratio of the partial pressure of the compound gas to the partial pressure of the simple gas may be made less than 1/2 by setting the ratio of the compound gas supply time to the single gas supply amount, or two or more of these, to less than 1/2. In these cases as well, the same effects as in the above embodiments can be obtained.
• the supply of the simple gas and the supply of the compound gas to the wafer 200 in step B are started and stopped at the same time, but the present disclosure is not limited thereto.
• the supply of the compound gas may be started before the supply of the simple gas, and then the simple gas and the compound gas may be supplied simultaneously. Further, in a state where the simple gas and the compound gas are supplied simultaneously, the supply of the compound gas may be stopped before the supply of the simple gas is stopped, and then the supply of the simple gas may be stopped. In these cases as well, the same effects as in the above embodiments can be obtained.
• the simple gas is plasma-excited in the remote plasma unit 300b and the compound gas is plasma-excited in the remote plasma unit 300c, and the active species X and the active species Z are individually processed through the nozzle 249b and the nozzle 249c, respectively.
• the active species X and the active species Z may be generated by mixing a simple gas and a compound gas in a supply pipe, and then plasma-exciting both the mixed gases in one remote plasma unit. In this case, a mixed gas of a simple gas and a compound gas containing active species X and active species Z is supplied to the wafer 200.
• the source gas is supplied in step A by flash flow
• the present disclosure is not limited thereto.
• the gas may be supplied in the same manner as the gas supply method in steps B and C. Also in this case, the same effects as in the above embodiment can be obtained.
• the recipes used for each process be prepared individually according to the content of the process and stored in the storage device 121c via a telecommunications 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 content of the process. This makes it possible to form films of various film types, composition ratios, film qualities, and film thicknesses with good reproducibility using one substrate processing apparatus. Furthermore, the burden on the operator can be reduced, and each process can be started quickly while avoiding operational errors.
• the above-mentioned recipe is not limited to the case where it is newly created, but may be prepared by, for example, changing an existing recipe that has already been installed in the substrate processing apparatus.
• the changed recipe may be installed in the substrate processing apparatus via a telecommunications line or a recording medium on which the recipe is recorded.
• 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.
• each process can be performed under the same processing procedure and processing conditions as in the above embodiment, and the same effects as in the above embodiment can be obtained.
• the above embodiments can be used in appropriate combinations.
• the processing procedure and processing conditions at this time can be, for example, the same as the processing procedure and processing conditions of the above embodiment.
• Example 2 Using the substrate processing apparatus described above, the following film formation sequence was performed to form a SiN film on a wafer, and samples 1 to 6 were manufactured (see FIG. 5).
• Sample 1 (raw material gas ⁇ purge ⁇ plasma excited reaction gas ⁇ purge) ⁇ n
• Sample 2 (raw material gas ⁇ purge ⁇ plasma excited reaction gas ⁇ purge) ⁇ n
• Sample 3 (raw material gas ⁇ purge ⁇ plasma-excited compound gas ⁇ plasma-excited reaction gas ⁇ purge) ⁇ n
• Sample 4 (raw material gas ⁇ purge ⁇ plasma-excited simple gas ⁇ plasma-excited reaction gas ⁇ purge) ⁇ n
• Sample 5 (raw material gas ⁇ purge ⁇ plasma-excited simple gas/compound gas ⁇ plasma-excited reaction gas ⁇ purge) ⁇ n
• Sample 6 (raw material gas ⁇ purge ⁇ plasma-excited simple gas/compound gas ⁇ plasma-excited reaction gas ⁇ purge) ⁇ n
• FIG. 5 shows that active species X, active species Y, and active species Z were supplied by exciting a simple gas, a reactive gas, and a compound gas, respectively.
• DCS gas was used as the source gas
• H 2 gas was used as the simple gas
• NH 3 gas was used as the compound gas and reaction gas
• N 2 gas was used as the inert gas.
• N 2 gas was used as the simple gas.
• the processing conditions were predetermined conditions within the range of processing conditions in each step shown in the above embodiment.
• the purge time performed after supplying the raw material gas was set to be 30 seconds, which was a long time.
• the vertical axis in FIG. 6 indicates the WER ( ⁇ /min) of the SiN film with respect to 1% concentration hydrofluoric acid (1% HF aqueous solution).
• the horizontal axis in FIG. 6 indicates a predetermined position of the SiN film on the diameter of a wafer having a diameter of 300 mm.
• -150 (mm) is one end on the diameter of the wafer
• 0 (mm) is the midpoint of the wafer diameter (center point of the wafer)
• 150 (mm) is the other end on the diameter of the wafer.
• the ends are shown respectively.
• ⁇ , ⁇ , ⁇ , ⁇ , ⁇ in FIG. 6 indicate the measurement results of samples 1 to 6 in order.
• sample 1 had the highest WER. It was also confirmed that sample 2 had the second highest WER and sample 3 had the third highest WER. From these results, it was found that even if the purge time after supplying the raw material gas was lengthened, or even if the compound gas was supplied after supplying the raw material gas, the WER could not be significantly lowered.
• Sample 5 was able to lower WER and maintain good in-plane uniformity compared to Samples 1 to 3. Specifically, it was confirmed that Sample 5 was able to maintain the difference in WER between the outer periphery and the center of the wafer within 2 ⁇ /min. From the above, it has been found that by supplying both the simple gas and the compound gas after supplying the raw material gas, WER can be lowered and in-plane uniformity can also be maintained favorably. Note that the ratio of WER between the outer periphery and the center of the wafer (outer periphery)/(center) is preferably 0.80 or more and 1.20 or less.
• sample 6 also gave the same results as sample 5. This revealed that the same results as Sample 5 can be obtained even when N 2 gas is used as the simple gas.
• the vertical axis in FIG. 7 indicates the Cl concentration (atoms/cm 3 ) in the SiN film.
• the horizontal axis in FIG. 7 indicates the WER ( ⁇ /min) of the SiN film with respect to 1% concentration hydrofluoric acid (1% HF aqueous solution).
• ⁇ , ⁇ , ⁇ , and ⁇ in FIG. 7 are, in order, WER and Cl concentration at the outer periphery of the wafer of sample 4, WER and Cl concentration at the center of the wafer of sample 4, and WER at the outer periphery of the wafer of sample 5. and Cl concentration, and the WER and Cl concentration at the center of the wafer of sample 5.
• sample 4 it was confirmed that the difference in WER between the outer peripheral part and the central part of the wafer was relatively large, that is, the in-plane uniformity was poor.
• sample 5 it was confirmed that the difference in WER between the outer peripheral part and the central part of the wafer was relatively small, that is, the in-plane uniformity was good.

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