Classifications

• • 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
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
  • H10P50/282—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials
  • H10P50/283—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials by chemical means
• • 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
• • 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
  • C23C16/22—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
  • C23C16/36—Carbonitrides
• • 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
  • 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
  • H10P14/69—Inorganic materials
  • H10P14/6903—Inorganic materials containing silicon
  • H10P14/6905—Inorganic materials containing silicon being a silicon carbide or silicon carbonitride and not containing oxygen, e.g. SiC or SiC:H
• • 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
• • 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
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/60—Wet etching
  • H10P50/64—Wet etching of semiconductor materials
  • H10P50/642—Chemical etching
• • 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
  • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
  • H10P72/04—Apparatus for manufacture or treatment
  • H10P72/0402—Apparatus for fluid treatment
  • H10P72/0418—Apparatus for fluid treatment for etching
  • H10P72/0421—Apparatus for fluid treatment for etching for drying etching
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W20/00—Interconnections in chips, wafers or substrates
  • H10W20/01—Manufacture or treatment
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W20/00—Interconnections in chips, wafers or substrates
  • H10W20/01—Manufacture or treatment
  • H10W20/071—Manufacture or treatment of dielectric parts thereof
  • H10W20/072—Manufacture or treatment of dielectric parts thereof of dielectric parts comprising air gaps
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W20/00—Interconnections in chips, wafers or substrates
  • H10W20/40—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes
  • H10W20/45—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes characterised by their insulating parts
  • H10W20/48—Insulating materials thereof

Definitions

• the present disclosure relates to a substrate processing method, a semiconductor device manufacturing method, a substrate processing system, and a program.
• a process for forming air gaps on a substrate may be performed (see, for example, Patent Document 1).
• This disclosure provides technology that allows for precise formation of air gaps with high accuracy.
• exposing a surface of the substrate on which the third film is formed on the first film and the second film to an etching agent that reacts with the first film, thereby removing the first film while retaining the second film and the third film;
• This disclosure makes it possible to precisely form air gaps with high accuracy.
• FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing system suitably used in each aspect of the present disclosure, showing a processing furnace portion in vertical cross section.
• FIG. 2 is a schematic configuration diagram of a vertical processing furnace of a substrate processing system preferably used in each aspect of the present disclosure, and shows a cross-sectional view of the processing furnace portion taken along line AA of FIG.
• FIG. 3 is a schematic configuration diagram of a controller of a substrate processing system preferably used in each aspect 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 sequence according to one aspect of the present disclosure.
• FIG. 5(a) is a partial cross-sectional enlarged view of a surface portion of a wafer in an embodiment of the present disclosure having a first film and a second film on the surface.
• FIG. 5(b) is a partial cross-sectional enlarged view of a surface portion of a wafer in an embodiment of the present disclosure after forming an initial layer on the first film and the second film.
• FIG. 5(c) is a partial cross-sectional enlarged view of a surface portion of a wafer in an embodiment of the present disclosure after forming a third film on the initial layer.
• FIG. 5(d) is a partial cross-sectional enlarged view of a surface portion of a wafer in an embodiment of the present disclosure after forming an air gap by removing the first film while retaining the second and third films.
• FIG. 5(e) is a partial cross-sectional enlarged view of a surface portion of a wafer in an embodiment of the present disclosure after forming a fourth film on the third film.
• FIG. 6(a) is a partial cross-sectional enlarged view of a surface portion of a wafer in another embodiment of the present disclosure having a first film and a second film on the surface.
• FIG. 6(b) is a partial cross-sectional enlarged view of a surface portion of a wafer in another embodiment of the present disclosure after forming an initial layer on the first film and the second film.
• FIG. 6(c) is a partial cross-sectional enlarged view of a surface portion of a wafer in another embodiment of the present disclosure after forming a third film on the initial layer.
• FIG. 6(d) is a partial cross-sectional enlarged view of a surface portion of a wafer in another embodiment of the present disclosure after forming an air gap by removing a portion of the first film while retaining the second and third films.
• FIG. 6(e) is a partial cross-sectional enlarged view of a surface portion of a wafer in another embodiment of the present disclosure after forming a fourth film on the third film.
• FIG. 7(a) is a TEM image of a surface portion of a wafer in an embodiment having a first film and a second film on the surface.
• FIG. 7(b) is a TEM image of a surface portion of a wafer in an embodiment after forming an initial layer and a third film on the first film and the second film.
• FIG. 7(c) is a TEM image of a surface portion of a wafer in an embodiment after exposing the surface of the wafer after forming the third film to an etching agent for 30 minutes.
• FIG. 7(d) is a TEM image of a surface portion of a wafer in an embodiment after exposing the surface of the wafer after forming the third film to an etching agent for 60 minutes.
• FIG. 7(e) is a TEM image of a surface portion of a wafer in an embodiment after exposing the surface of the wafer after forming the third film to an etching agent for 90 minutes.
• FIG. 7(f) is a TEM image of a surface portion of a wafer in an embodiment after exposing the surface of the wafer after forming the third film to an etching agent for 25 minutes and then forming a fourth film on the third film.
• FIG. 7( g ) is a TEM image of a surface portion of a wafer in an example after forming a fourth film on the third film after forming multiple air gaps by removing portions of the first film while retaining the second and third films.
• the processing furnace 202 has a heater 207 as a heating mechanism (temperature adjustment unit).
• the heater 207 is cylindrical and is installed vertically by being supported by a holding plate.
• 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 material 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 wafer 200 as a substrate. In the processing chamber 201, processing of the wafer 200 is performed.
• Nozzles 249a to 249c serving as first to third supply units are provided within the processing chamber 201, penetrating the sidewall of the manifold 209, respectively. Nozzles 249a to 249c are also referred to as first to third nozzles, respectively. 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 nozzles 249a to 249c, respectively. Nozzles 249a to 249c are different nozzles, and each of nozzles 249a, 249c is provided adjacent to nozzle 249b.
• Gas supply pipes 232a to 232c are provided with mass flow controllers (MFCs) 241a to 241c, which are flow rate control devices (flow rate control parts), and valves 243a to 243c, which are on-off valves, in order from the upstream side of the gas flow.
• MFCs mass flow controllers
• Gas supply pipe 232e is connected to the downstream side of valve 243a of gas supply pipe 232a.
• Gas supply pipes 232d and 232f are connected to the downstream side of valve 243b of gas supply pipe 232b.
• Gas supply pipe 232g is connected to the downstream side of valve 243c of gas supply pipe 232c.
• Gas supply pipes 232d to 232g are provided with MFCs 241d to 241g and valves 243d to 243g in order from the upstream side of the gas flow.
• Gas supply pipes 232a to 232g are made of a metal material, such as SUS.
• the nozzles 249a to 249c are provided in a circular space between the inner wall of the reaction tube 203 and the wafers 200 in a plan view, from the lower part to the upper part of the inner wall of the reaction tube 203, so as to rise upward in the arrangement direction of the wafers 200. That is, the nozzles 249a to 249c are provided in a region that surrounds the wafer arrangement region horizontally to the side of the wafer arrangement region in which the wafers 200 are arranged, so as to follow the wafer arrangement region. In a plan view, the nozzle 249b is arranged to face the exhaust port 231a (described later) in a straight line across the center of the wafer 200 that is loaded into the processing chamber 201.
• the nozzles 249a and 249c are arranged to sandwich the straight line L that passes through the nozzle 249b and the center of the exhaust port 231a from both sides along the inner wall of the reaction tube 203 (the outer periphery of the wafers 200).
• Line L is also a line passing through nozzle 249b and the center of wafer 200.
• nozzle 249c can be said to be provided on the opposite side of nozzle 249a across line L.
• Nozzles 249a and 249c are arranged symmetrically with line L as the axis of symmetry.
• Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of nozzles 249a to 249c, respectively.
• Each of gas supply holes 250a to 250c opens so as to face exhaust port 231a in plan view, and is capable of supplying gas toward wafer 200.
• a plurality of gas supply holes 250a to 250c are provided from the lower part to the upper part of reaction tube 203.
• the raw material serving as the film forming agent is supplied from the gas supply pipe 232a into the processing chamber 201 via the MFC 241a, the valve 243a, and the nozzle 249a.
• the first reactant which serves as a film forming agent, is supplied from the gas supply pipe 232b into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.
• the second reactant which serves as a film forming agent, is supplied from the gas supply pipe 232c into the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c.
• the etching agent is supplied from the gas supply pipe 232d through the MFC 241d, the valve 243d, the gas supply pipe 232b, and the nozzle 249b into the processing chamber 201.
• Inert gas is supplied from gas supply pipes 232e to 232g into the processing chamber 201 via MFCs 241e to 241g, valves 243e to 243g, gas supply pipes 232a to 232c, and nozzles 249a to 249c.
• the inert gas acts as a purge gas, carrier gas, dilution gas, etc.
• the raw material supply system is mainly composed of gas supply pipe 232a, MFC 241a, and valve 243a.
• the first reactant supply system is mainly composed of gas supply pipe 232b, MFC 241b, and valve 243b.
• the second reactant supply system is mainly composed of gas supply pipe 232c, MFC 241c, and valve 243c.
• the etching agent supply system (etching agent exposure system) is mainly composed of gas supply pipe 232d, MFC 241d, and valve 243d.
• the inert gas supply system is mainly composed of gas supply pipes 232e to 232g, MFCs 241e to 241g, and valves 243e to 243g.
• any or all of the various supply systems described above may be configured as an integrated supply system 248 in which valves 243a to 243g and MFCs 241a to 241g are integrated.
• the integrated supply system 248 is connected to each of the gas supply pipes 232a to 232g, and is configured so that the supply operation of various substances (various gases) into the gas supply pipes 232a to 232g, i.e., the opening and closing operation of the valves 243a to 243g and the flow rate adjustment operation by the MFCs 241a to 241g, 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 232g, 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.
• An exhaust port 231a for exhausting the atmosphere in the processing chamber 201 is provided at the bottom of the side wall of the reaction tube 203. As shown in FIG. 2, the exhaust port 231a is provided at a position facing the nozzles 249a to 249c (gas supply holes 250a to 250c) across the wafer 200 in a plan view. The exhaust port 231a may be provided along the side wall of the reaction tube 203 from the bottom to the top, that is, along the wafer arrangement area. An exhaust pipe 231 is connected to the exhaust port 231a.
• 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) that detects 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 is configured to be able to evacuate and stop the evacuation of the processing chamber 201 by opening and closing the valve while the vacuum pump 246 is operating, and further, to be able to adjust the pressure inside the processing chamber 201 by adjusting the valve opening based on pressure information detected by the pressure sensor 245 while the vacuum pump 246 is operating.
• 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 considered to be included in the exhaust system.
• a seal cap 219 is provided as a furnace port cover body capable of airtightly closing the lower end opening of the manifold 209.
• the seal cap 219 is made of a metal material 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 to rotate the boat 217 described later.
• 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 vertically by a boat elevator 115 as a lifting mechanism installed outside the reaction tube 203.
• the boat elevator 115 is configured as a transport device (transport mechanism) that transports the wafers 200 in and out of the processing chamber 201 by raising and lowering the seal cap 219.
• a shutter 219s is provided as a furnace port cover that can airtightly close the lower end opening of the manifold 209 when the seal cap 219 is lowered and the boat 217 is removed from the processing chamber 201.
• the shutter 219s is made of a metal material such as SUS and is formed in a disk shape.
• An O-ring 220c is provided on the upper surface of the shutter 219s as a sealing member that abuts against the lower end of the manifold 209.
• the opening and closing operation of the shutter 219s (lifting and lowering operation, rotation operation, etc.) is controlled by a shutter opening and closing mechanism 115s.
• 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 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 equipped with 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.
• an external storage device 123 can be connected to the controller 121.
• the storage device 121c is composed of, for example, a flash memory, a HDD (Hard Disk Drive), an SSD (Solid State Drive), etc.
• a control program for controlling the operation of the substrate processing device, a process recipe describing the procedures and conditions of the substrate processing described later, etc. are recorded and stored in a readable manner.
• the process recipe is a combination of procedures in the substrate processing described later that are executed by the controller 121 in the substrate processing device 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 when used, 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 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.
• 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 substances (various gases) by the MFCs 241a to 241g, the opening and closing of the valves 243a to 243g, the opening and closing of the APC valve 244 and the pressure adjustment by the APC valve 244 based on the pressure sensor 245, the start and stop of the vacuum pump 246, the temperature adjustment of the heater 207 based on the temperature sensor 263, the rotation and rotation speed adjustment of the boat 217 by the rotation mechanism 267, the raising and lowering of the boat 217 by the boat elevator 115, the opening and closing of the shutter 219s by the shutter opening and closing mechanism 115s, etc.
• the controller 121 can be configured by installing the above-mentioned program recorded and 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 USB memory, a semiconductor memory such as an SSD, etc.
• the storage device 121c and the external storage device 123 are configured as computer-readable recording media. Hereinafter, these are collectively referred to simply as recording media.
• recording medium 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.
• the wafer 200 has a first film and a second film on the surface.
• the first film is a film (first base) containing a semiconductor element and oxygen
• the second film is a film (second base) containing a semiconductor element and nitrogen or a metal element.
• the first film is a silicon oxide film ( SiO2 film, hereinafter also referred to as a SiO film) containing silicon (Si) and oxygen (O) as semiconductor elements
• the second film is a silicon nitride film ( Si3N4 film, hereinafter also referred to as a SiN film) containing silicon (Si) and nitrogen ( N ) as semiconductor elements.
• a third film on the first film and the second film by supplying a source material, a first reactant, and a second reactant to a wafer 200 having a first film and a second film on a surface thereof under conditions in which, when the source material exists alone, the source material is not thermally decomposed and physical adsorption of the source material occurs predominantly over chemical adsorption of the source material (third film formation);
• a step (etching) of removing the first film while retaining the second and third films by exposing the surface of the wafer 200, on which the third film has been formed on the first and second films, to an etching agent that reacts with the first film.
• the step of forming an initial layer on the first film and the second film is performed by supplying the raw material and the first reactant or the second reactant under conditions in which chemical adsorption or thermal decomposition of the raw material occurs more predominantly than physical adsorption when the raw material exists alone. That is, in this embodiment, an initial layer is formed on the first film and the second film, and a third film is formed on the initial layer. Note that, depending on the material of the first film and the second film, the initial layer formation can be omitted. When the initial layer formation is omitted, the third film is directly formed on the first film and the second film.
• a cycle including step A1 of supplying a raw material to the wafer 200 and step A2 of supplying a first reactant or a second reactant to the wafer 200 is performed a predetermined number of times (n 1 times, n 1 is an integer of 1 or 2 or more) at a first temperature.
• Fig. 4 shows a case in which the second reactant is supplied to the wafer 200 in step A2.
• a cycle including step B1 of simultaneously supplying a raw material and a first reactant to the wafer 200 and step B2 of supplying a second reactant to the wafer 200 is performed a predetermined number of times (n 2 times, n 2 is an integer of 1 or 2 or more) at a second temperature lower than the first temperature to form a film having fluidity (hereinafter also referred to as a fluid film) on the initial layer (fluid film formation); a step (post-treatment) of heat-treating the wafer 200 on which the fluid film has been formed at a third temperature higher than the second temperature to modify the fluid film into a film having no fluidity (hereinafter also referred to as a non-fluid film); In this specification, post-treatment is also referred to as PT.
• a cycle including step C1 of supplying a raw material to the wafer 200 and step C2 of supplying a first reactant or a second reactant to the wafer 200 is performed a predetermined number of times (n 3 times, n 3 is an integer of 1 or 2 or more) at a third temperature higher than the second temperature.
• Fig. 4 shows a case in which the second reactant is supplied to the wafer 200 in step C2.
• the timing of supplying the raw material, the first reactant, and the second reactant can be changed as appropriate.
• Third film formation (raw material ⁇ first reactant ⁇ second reactant) ⁇ n 2 ⁇ PT
• 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.
• agent includes at least one of a gaseous substance and a liquid substance.
• Liquid substances include mist substances. That is, each of the film-forming agents (raw material, first reactant, second reactant) and the etching agent may contain a gaseous substance, may contain a liquid substance such as a mist substance, or may contain both.
• the term "layer” includes at least one of a continuous layer and a discontinuous layer.
• the layers formed in each step described below may include a continuous layer, a discontinuous layer, or both.
• the first film and the second film are alternately arranged adjacent to each other, as shown in FIG. 5(a).
• a case will be described in which the first film and the second film are alternately arranged parallel to the flat surface of the wafers 200.
• the first film is a SiO film and the second film is a SiN film, as described above.
• the inside of the processing chamber 201 i.e., the space in which the wafer 200 is present, is evacuated (reduced pressure exhaust) by the vacuum pump 246 so that the inside of the processing chamber 201 is at 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 wafer 200 in the processing chamber 201 is heated by the heater 207 so that the processing temperature is at a desired processing temperature.
• the power supply to the heater 207 is feedback-controlled based on the temperature information detected by the temperature sensor 263 so that the inside of the processing chamber 201 has a desired temperature distribution (temperature adjustment).
• the rotation mechanism 267 starts rotating the wafer 200. The evacuation inside the processing chamber 201 and the heating and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.
• step A 1 a raw material is supplied to the wafer 200 in the processing chamber 201 .
• valve 243a is opened to allow the raw material to flow into gas supply pipe 232a.
• the raw material has its flow rate adjusted by MFC 241a, is supplied into processing chamber 201 via nozzle 249a, and is exhausted from exhaust port 231a. At this time, the raw material is supplied to wafer 200 (raw material supply).
• valves 243e to 243g may be opened to supply an inert gas into processing chamber 201 via nozzles 249a to 249c, respectively.
• valve 243a is closed to stop the supply of raw materials into processing chamber 201. Then, processing chamber 201 is evacuated to remove gaseous substances remaining in processing chamber 201 from processing chamber 201. At this time, valves 243e to 243g are opened to supply inert gas into processing chamber 201 through nozzles 249a to 249c. The inert gas supplied from nozzles 249a to 249c acts as a purge gas, and the space in which wafer 200 exists, i.e., processing chamber 201, is purged (purged).
• a silane-based gas containing silicon (Si) can be used as a raw material.
• a silane-based gas for example, a gas containing Si and a halogen, i.e., a halosilane-based gas, can be used.
• Halogen includes chlorine (Cl), fluorine (F), bromine (Br), iodine (I), etc. That is, the halosilane-based gas includes a chlorosilane-based gas, a fluorosilane-based gas, a bromosilane-based gas, an iodosilane-based gas, etc.
• halosilane-based gas for example, a gas containing silicon, carbon (C), and a halogen, i.e., an organic halosilane-based gas can be used.
• a gas containing Si, C, and Cl i.e., an organic chlorosilane-based gas can be used.
• Examples of the raw material include C- and halogen-free silane gases such as monosilane (SiH 4 ) gas and disilane (Si 2 H 6 ) gas, C-free halosilane gases such as dichlorosilane (SiH 2 Cl 2 ) gas and hexachlorodisilane (Si 2 Cl 6 ) gas, alkylsilane gases such as trimethylsilane (SiH(CH 3 ) 3 ) gas, dimethylsilane (SiH 2 (CH 3 ) 2 ) gas, triethylsilane (SiH(C 2 H 5 ) 3 ) gas and diethylsilane (SiH 2 (C 2 H 5 ) 2 ) gas, bis(trichlorosilyl)methane ((SiCl 3 ) 2 CH 2 ) gas and 1,2-bis(trichlorosilyl)ethane ((SiCl 3 ) 2 C 2 H
• Examples of the raw material include (dimethylamino)trimethylsilane ((CH 3 ) 2 NSi(CH 3 ) 3 ) gas, (diethylamino)triethylsilane ((C 2 H 5 ) 2 NSi(C 2 H 5 ) 3 ) gas, (dimethylamino)triethylsilane ((CH 3 ) 2 NSi(C 2 H 5 ) 3 ) gas, (diethylamino)trimethylsilane ((C 2 H 5 ) 2 NSi(CH 3 ) 3 ) gas, (trimethylsilyl)amine ((CH 3 ) 3 SiNH 2 ) gas, (triethylsilyl)amine ((C 2 H 5 ) 3 SiNH 2 ), (dimethylamino)silane ((CH 3 ) 2 NSiH 3 ) gas, (diethylamino)silane ((C 2 H 5 ) Alkylaminosilane-based
• Some of these raw materials do not contain amino groups but contain halogens. Some of these raw materials contain chemical bonds between silicon and silicon (Si-Si bonds). Some of these raw materials contain silicon and halogens, or silicon, halogens, and carbon. Some of these raw materials contain alkyl groups and halogens. In other words, some of these raw materials contain halogen groups and alkyl groups.
• nitrogen ( N2 ) gas or a rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas, etc. can be used. This also applies to each step described later.
• argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas, etc. can be used. This also applies to each step described later.
• nitrogen ( N2 ) gas or a rare gas such as argon (Ar) gas, helium (He) gas, neon (Ne) gas, xenon (Xe) gas, etc.
• step A2 a first reactant or a second reactant is supplied to the wafer 200 in the process chamber 201 .
• the valve 243b When supplying the first reactant to the wafer 200, the valve 243b is opened and the first reactant is allowed to flow into the gas supply pipe 232b. The flow rate of the first reactant is adjusted by the MFC 241b, and the first reactant is supplied into the processing chamber 201 via the nozzle 249b and exhausted from the exhaust port 231a. At this time, the first reactant is supplied to the wafer 200 (first reactant supply). At this time, the valves 243e to 243g may be opened to supply an inert gas into the processing chamber 201 via each of the nozzles 249a to 249c.
• the valve 243c is opened and the second reactant is flowed into the gas supply pipe 232c.
• the flow rate of the second reactant is adjusted by the MFC 241c, and the second reactant is supplied into the processing chamber 201 via the nozzle 249c and exhausted from the exhaust port 231a.
• the second reactant is supplied to the wafer 200 (second reactant supply).
• the valves 243e to 243g may be opened to supply an inert gas into the processing chamber 201 via each of the nozzles 249a to 249c.
• valve 243b or 243c is closed to stop the supply of the first reactant or the second reactant into processing chamber 201. Then, gaseous substances remaining in processing chamber 201 are removed from processing chamber 201 by a processing procedure similar to the purging in step A1.
• the first reactant and the second reactant may both be, for example, a nitrogen (N) and hydrogen (H) containing gas.
• the first reactant and the second reactant may have the same molecular structure or may have different molecular structures.
• N- and H-containing gases include hydrogen nitride gases such as ammonia (NH 3 ) gas, ethylamine gases such as monoethylamine (C 2 H 5 NH 2 ) gas, diethylamine ((C 2 H 5 ) 2 NH) gas, and triethylamine ((C 2 H 5 ) 3 N) gas, methylamine gases such as monomethylamine (CH 3 NH 2 ) gas, dimethylamine ((CH 3 ) 2 NH) gas, and trimethylamine ((CH 3 ) 3 N) gas, pyridine (C 5 H 5 N) gas, piperazine (C 4 H 10 N 2 ) gas, and cyclic amine gases such as monomethylhydrazine ((CH 3 ) HN 2 H
• amine gases and organic hydrazine gases are composed of C, N, and H, these gases can also be called C-, N-, and H-containing gases.
• the amine gas containing the above-mentioned alkyl group can also be called alkylamine gas.
• a C-containing gas (C- and H-containing gas) such as ethylene (C 2 H 4 ) gas, acetylene (C 2 H 2 ) gas, or propylene (C 3 H 6 ) gas and an N-containing gas (N- and H-containing gas) such as NH 3 gas can be supplied simultaneously or non-simultaneously.
• the first reactant and the second reactant one or more of these N- and H-containing reactants or C-, N-, and H-containing reactants can be used.
• the first reactant comprises an alkyl group, and more preferably, an amine or an organic hydrazine.
• the above-mentioned cycle is performed a predetermined number of times under conditions in which, when the raw material is present alone, chemical adsorption or thermal decomposition of the raw material occurs more predominantly than physical adsorption of the raw material.
• the processing conditions for supplying the raw material in step A1 are as follows: Treatment temperature (first temperature): 350 to 700°C, more preferably 450 to 650°C Treatment pressure: 1 to 2666 Pa, preferably 67 to 1333 Pa Raw material supply flow rate: 0.001 to 2 slm, preferably 0.01 to 1 slm Raw material supply time: 1 to 120 seconds, preferably 1 to 60 seconds Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm, preferably 0.01 to 10 slm Examples are given below.
• the process temperature means the temperature of the wafer 200 or the temperature inside the process chamber 201
• the process pressure means the pressure inside the process chamber 201.
• a gas supply flow rate of 0 slm means that the gas is not supplied.
• the process conditions for supplying the first reactant or the second reactant in step A2 are as follows: Treatment pressure: 1 to 4000 Pa, preferably 1 to 3000 Pa First reactant or second reactant supply flow rate: 0.001 to 20 slm, preferably 1 to 10 slm
• the supply time of the first reactant or the second reactant is, for example, 1 to 120 seconds, preferably 1 to 60 seconds.
• Other processing conditions can be the same as the processing conditions when the raw materials are supplied in step A1.
• a part of the molecular structure of the raw material molecules can be adsorbed on the surface of the wafer 200, i.e., the surface of the first film and the second film, in step A1. Also, by supplying the first reactant or the second reactant under the above-mentioned processing conditions in step A2, a part of the molecular structure of the raw material molecules adsorbed on the surface of the first film and the second film can be reacted with the first reactant or the second reactant to be modified and form a layer with no fluidity (hereinafter also referred to as a non-fluidity layer).
• a non-fluidity layer of a predetermined thickness can be formed as an initial layer on the first film and the second film, as shown in FIG. 5(b).
• the initial layer becomes a continuous layer that conformally covers the surfaces of the first film and the second film.
• the above cycle is preferably repeated multiple times. In other words, it is preferable to make the thickness of the non-fluid layer formed per cycle thinner than the desired thickness, and to repeat the above cycle multiple times until the thickness of the initial layer formed by stacking the non-fluid layers reaches the desired thickness.
• the thickness of the initial layer is preferably equal to or less than the thickness of the fluid film described below, or thinner than the thickness of the fluid film described below. It is desirable for the thickness of the initial layer to be, for example, 0.2 nm or more and 5 nm or less, preferably 0.3 nm or more and 3 nm or less.
• the initial layer can be, for example, a Si- and N-containing layer such as a silicon nitride layer (SiN layer) or a Si-, C- and N-containing layer such as a silicon carbonitride layer (SiCN layer). Since the various raw materials and reactants described above do not contain oxygen (O), the initial layer is an O-free layer.
• the initial layer is less hydrophilic than the first film (O-containing film) on the surface of the wafer 200.
• the first film which is part of the base for film formation, is a hydrophilic film, it is preferable to make the initial layer a non-hydrophilic layer (hydrophobic layer).
• a third film is formed, which includes the following two steps: flowable film formation and post-treatment.
• the output of the heater 207 is adjusted so as to change the temperature of the wafer 200 to a second temperature lower than the first temperature (temperature drop). Then, when the temperature of the wafer 200 becomes stable at the second temperature, the following steps B1 and B2 are performed.
• step B1 the source material and the first reactant are simultaneously supplied to the wafer 200 in the processing chamber 201.
• the process procedure for supplying the source material and the process procedure for supplying the first reactant can be the same as the process procedures described in steps A1 and A2 above, respectively.
• valves 243a and 243b are closed to stop the supply of the raw material and the first reactant into the processing chamber 201. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 by a processing procedure similar to the purging in step A1.
• a specific raw material can be arbitrarily selected from the various raw materials exemplified in step A1.
• the raw material used in step B1 and the raw material used in step A1 may have the same molecular structure or may have different molecular structures.
• a specific reactant can be arbitrarily selected from the various reactants exemplified in step A2.
• the reactant used in step B1 and the reactant used in step A2 may have the same molecular structure or different molecular structures.
• Step B2 a second reactant is supplied to the wafer 200 in the process chamber 201.
• the procedure for supplying the second reactant may be the same as the procedure described in step A2 above.
• valve 243c is closed to stop the supply of the second reactant into processing chamber 201. Then, gases remaining in processing chamber 201 are removed from processing chamber 201 by a processing procedure similar to the purging in step A1.
• a specific reactant can be arbitrarily selected from the various reactants exemplified in step A2.
• the reactant used in step B2 and the reactants used in steps A1 and B1 may have the same molecular structure or different molecular structures.
• the above-mentioned cycle is performed a predetermined number of times under conditions in which, when the raw material is present alone, the raw material is not thermally decomposed and the physical adsorption of the raw material occurs more predominantly than the chemical adsorption of the raw material.
• the processing conditions for supplying the raw material and the first reactant in step B1 are as follows: Treatment temperature (second temperature): 0 to 150°C, preferably 10 to 100°C, more preferably 20 to 60°C Treatment pressure: 10 to 6000 Pa, preferably 50 to 2000 Pa Raw material supply flow rate: 0.01 to 1 slm First reactant feed flow rate: 0.01-5 slm Raw material and first reactant supply time: 1 to 300 seconds Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm, preferably 0.01 to 10 slm Examples are given below.
• the process conditions for supplying the second reactant in step B2 are as follows: Second reactant supply flow rate: 0.01-5 slm Second reactant supply time: 1 to 300 seconds Other process conditions may be the same as those in step B1 when the raw material and the first reactant are supplied.
• oligomers containing elements contained in at least one of the raw material, the first reactant, and the second reactant can be generated, grown, and flowed on the first and second films, i.e., on the initial layer formed on the first and second films, and a continuous oligomer-containing film can be formed as a flowable film on the initial layer.
• the oligomer refers to a polymer having a relatively low molecular weight (e.g., a molecular weight of 10,000 or less) to which a relatively small number of monomers (e.g., 10 to 100) are bonded.
• the flowable film becomes a film containing various elements such as Si, Cl, and N, and substances represented by the chemical formula C x H 2x+1 (x is an integer of 1 to 3), such as CH 3 and C 2 H 5 .
• the above-mentioned processing temperature is set below 0°C, the raw material supplied into the processing chamber 201 is likely to liquefy, and it may be difficult to supply the raw material in a gaseous state to the wafer 200. In this case, the reaction for forming the above-mentioned fluid film may not proceed smoothly, and it may be difficult to form a fluid film on the initial layer.
• This problem can be solved by setting the processing temperature to 0°C or higher. This problem can be sufficiently solved by setting the processing temperature to 10°C or higher, and this problem can be even more sufficiently solved by setting the processing temperature to 20°C or higher.
• the processing temperature is higher than 150°C, the reaction to form the above-mentioned fluid film may not proceed smoothly. In this case, the oligomers formed on the initial layer may be more likely to detach than grow, making it difficult to form a fluid film on the initial layer.
• This problem can be solved by setting the processing temperature to 150°C or lower. This problem can be solved sufficiently by setting the processing temperature to 100°C or lower, and this problem can be solved even more sufficiently by setting the processing temperature to 60°C or lower.
• the processing temperature is desirable to between 0°C and 150°C, preferably between 10°C and 100°C, and more preferably between 20°C and 60°C.
• the output of the heater 207 is adjusted (heating up) so as to change the temperature of the wafer 200 to a third temperature equal to or higher than the second temperature described above, preferably to a third temperature higher than the second temperature described above. Then, when the temperature of the wafer 200 has reached the third temperature and is stable, a post-treatment (PT) is performed.
• PT post-treatment
• an inert gas is supplied to the wafer 200 in the processing chamber 201.
• the valves 243e to 243g are opened to allow the inert gas to flow into the gas supply pipes 232e to 232g.
• the flow rate of the inert gas is adjusted by the MFCs 241e to 241g, and the inert gas is supplied into the processing chamber 201 via the nozzles 249a to 249c and exhausted from the exhaust port 231a. At this time, the inert gas is supplied to the wafer 200.
• Treatment temperature third temperature: 100 to 1000°C, preferably 200 to 600°C
• Treatment pressure 10 to 80,000 Pa, preferably 200 to 6,000 Pa
• Inert gas supply flow rate 0.01 to 2 slm
• Inert gas supply time 300 to 10,800 seconds is exemplified.
• a Si, C and N-containing film such as a SiCN film or a Si and N-containing film such as a SiN film can be formed as a third film on the initial layer.
• the third film becomes a continuous film that conformally covers the surfaces of the first film and the second film, i.e., the surface of the initial layer formed on the first film and the second film.
• the third film is a fluid film at least during its formation process, but is changed to a non-fluid film by carrying out PT.
• the term "third film” may include a film that has been changed from a fluid film to a non-fluid film by carrying out PT, a fluid film before carrying out PT, or both. It is desirable that the thickness of the third film formed through fluid film formation and PT is, for example, 0.2 nm to 20 nm, preferably 0.5 nm to 10 nm.
• an H-containing gas such as hydrogen (H 2 ) gas may be supplied to the wafer 200
• an N-containing gas such as NH 3 gas, i.e., an N- and H-containing gas
• an O-containing gas such as H 2 O gas, i.e., an O- and H-containing gas
• O 2 gas may be supplied as the O-containing gas.
• at least one of an N-containing gas, an H-containing gas, an N- and H-containing gas, an O-containing gas, and an O- and H-containing gas may be supplied to the wafer 200.
• the processing conditions for supplying H-containing gas in the PT are as follows: H-containing gas supply flow rate: 0.01 to 3 slm Treatment pressure: 10 to 1000 Pa, preferably 200 to 800 Pa Other treatment conditions may be the same as those described above when PT is performed under an inert gas atmosphere.
• N and H-containing gas supply flow rate 10 to 10,000 sccm
• Treatment pressure 10 to 6000 Pa, preferably 200 to 2000 Pa
• Other treatment conditions may be the same as those described above when PT is performed under an inert gas atmosphere.
• the processing conditions for supplying an O-containing gas in the PT are as follows: O-containing gas supply flow rate: 10 to 10,000 sccm Treatment pressure: 10 to 90,000 Pa, preferably 20,000 to 80,000 Pa Other treatment conditions may be the same as those described above when PT is performed under an inert gas atmosphere.
• the third film When PT is performed under an O-containing gas atmosphere, it is possible to make the third film contain O, and this film can be, for example, a silicon oxynitride film (SiON film) containing Si, O, and N, or a silicon oxynitride carbonitride film (SiOCN film) containing Si, O, C, and N.
• SiON film silicon oxynitride film
• SiOCN film silicon oxynitride carbonitride film
• etching After forming a third film, which is a non-fluid film, on the first and second films, i.e., on the initial layer formed on the first and second films, the output of the heater 207 is adjusted so as to change the temperature of the wafer 200 to a fourth temperature lower than the third temperature (temperature drop). Then, etching is performed in a state in which the temperature of the wafer 200 has become stable at the fourth temperature.
• etching the surface of the wafer 200 on which the third film is formed on the first and second films with the initial layer interposed therebetween is exposed to an etching agent that reacts with the first film.
• the valve 243d is opened and the etching agent is allowed to flow into the gas supply pipe 232d.
• the flow rate of the etching agent is adjusted by the MFC 241d, and the etching agent is supplied into the processing chamber 201 through the nozzle 249b and exhausted from the exhaust port 231a.
• the etching agent is supplied to the wafer 200 on which the third film is formed on the first and second films with the initial layer interposed therebetween (etching agent exposure).
• the valves 243e to 243g may be opened and an inert gas may be supplied into the processing chamber 201 through each of the nozzles 249a to 249c.
• valve 243d is closed to stop the supply of etching agent to processing chamber 201. Then, gases remaining in processing chamber 201 are removed from processing chamber 201 by a processing procedure similar to the purging in step A1.
• etching agent it is preferable to use a substance that is more reactive with the first film than with the second film, the initial layer, and the third film.
• a fluorine (F)-containing gas for example, a fluorine (F)-containing gas can be used.
• F-containing gas for example, chlorine trifluoride (ClF 3 ) gas, chlorine fluoride (ClF) gas, nitrogen fluoride (NF 3 ) gas, hydrogen fluoride (HF) gas, fluorine (F 2 ) gas, etc.
• various cleaning solutions can be used as the etching agent.
• an HF aqueous solution can be used as the etching agent to perform DHF cleaning.
• a cleaning solution containing ammonia water, hydrogen peroxide water, and pure water can be used as the etching agent to perform SC-1 cleaning (APM cleaning).
• a cleaning solution containing hydrochloric acid, hydrogen peroxide water, and pure water can be used as the etching agent to perform SC-2 cleaning (HPM cleaning).
• a cleaning solution containing sulfuric acid and hydrogen peroxide water can be used as the etching agent to perform SPM cleaning.
• the etching agent one or more of these can be used.
• the processing conditions when supplying the etching agent during etching are as follows: Treatment temperature (fourth temperature): room temperature (25°C) to 300°C, preferably 50 to 150°C Treatment pressure: 1 to 13332 Pa, preferably 100 to 3990 Pa Etching agent supply flow rate: 0.05 to 5 slm, preferably 0.1 to 2 slm Etching agent supply time: 0.1 to 3 hours, preferably 0.1 to 1 hour Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm, preferably 0.01 to 10 slm
• the etching agent supply time is synonymous with the etching agent exposure time.
• the etching agent penetrates the third film and further penetrates the initial layer to reach the first film and the second film.
• the second film is a SiN film containing nitrogen (N) or a film containing a metal element
• the second film has a higher etching resistance than the first film.
• the initial layer or the third film is a SiCN film containing carbon (C) in the form of, for example, Si-C bonds or Si-CH 3 bonds, or a SiN film containing nitrogen (N)
• the initial layer or the third film has a higher etching resistance than the first film.
• this step it is possible to selectively remove (etch) the first film while retaining the second film, the initial layer, and the third film.
• etch etch
• the amount of the first film removed i.e., the size of the air gap
• the size of the air gap formed on the surface of the wafer 200 can be expanded to a desired size.
• a fourth film is formed.
• the output of the heater 207 is adjusted (heating up) so as to change the temperature of the wafer 200 to a fifth temperature higher than the fourth temperature described above. Then, when the temperature of the wafer 200 becomes stable at the fifth temperature, the following steps C1 and C2 are performed.
• step C1 raw materials are supplied to the wafer 200 in the processing chamber 201.
• the processing procedure for supplying the raw materials may be the same as the processing procedure described in step A1 above.
• a predetermined raw material may be arbitrarily selected from the various raw materials exemplified in step A1.
• the raw materials used in step C1 and the raw materials used in step A1 may have the same molecular structure or may have different molecular structures.
• Step C2 a first reactant or a second reactant is supplied to the wafer 200 in the processing chamber 201.
• the procedure for supplying the first reactant or the second reactant may be the same as the procedure described in step A2 above.
• a predetermined reactant may be arbitrarily selected from the various reactants exemplified in step A2.
• the reactant used in step C2 and the reactant used in step A2 may have the same molecular structure or may have different molecular structures.
• the above-mentioned cycle is performed a predetermined number of times under conditions in which, when the raw material is present alone, chemical adsorption or thermal decomposition of the raw material occurs more predominantly than physical adsorption of the raw material.
• the processing conditions for supplying the raw material in step C1 are as follows: Treatment temperature (fifth temperature): 350 to 700°C, more preferably 450 to 650°C Treatment pressure: 1 to 2666 Pa, preferably 67 to 1333 Pa Raw material supply flow rate: 0.001 to 2 slm, preferably 0.01 to 1 slm Raw material supply time: 1 to 120 seconds, preferably 1 to 60 seconds Inert gas supply flow rate (per gas supply pipe): 0 to 20 slm, preferably 0.01 to 10 slm Examples are given below.
• the process conditions for supplying the first reactant or the second reactant in step C2 are as follows: Treatment pressure: 1 to 4000 Pa, preferably 1 to 3000 Pa First reactant or second reactant supply flow rate: 0.001 to 20 slm, preferably 1 to 10 slm
• the supply time of the first reactant or the second reactant is, for example, 1 to 120 seconds, preferably 1 to 60 seconds.
• Other processing conditions can be the same as the processing conditions when the raw material is supplied in step C1.
• a part of the molecular structure of the raw material molecules can be adsorbed on the surface of the third film in step C1. Also, by supplying the first reactant or the second reactant in step C2 under the above-mentioned processing conditions, a part of the molecular structure of the raw material molecules adsorbed on the surface of the third film can be reacted with the first reactant or the second reactant in step C2 to form a non-fluid layer. Then, by performing the above-mentioned cycle a predetermined number of times under the above-mentioned processing conditions, as shown in FIG.
• a Si- and N-containing film such as a SiN film or a Si
• C- and N-containing film such as a SiCN film
• the fourth film becomes a non-fluid film.
• the above-mentioned cycle is preferably repeated multiple times. In other words, it is preferable to make the thickness of the non-fluid layer formed per cycle thinner than the desired thickness, and to repeat the above-mentioned cycle multiple times until the thickness of the fourth film formed by laminating the non-fluid layers reaches the desired thickness.
• step C2 instead of the various reactants (N and H containing gas) exemplified in step A2, an O-containing gas such as H 2 O gas or O 2 gas can be supplied as the first reactant or the second reactant, and the above-mentioned O-containing gas can be further added to the various reactants exemplified in step A2.
• a silicon oxide film (SiO film), a silicon oxycarbide film (SiOC film), a silicon oxycarbonitride film (SiOCN film), or a silicon oxynitride film (SiON film) can be formed as the fourth film.
• a silicon film (Si film) can be formed as the fourth film.
• an inert gas is supplied as a purge gas from each of the nozzles 249a to 249c into the processing chamber 201, and exhausted from the exhaust port 231a. 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, and the lower end of the manifold 209 is opened. Then, the processed wafers 200 are carried out from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the boat 217 (boat unloading). After the boat unloading, the shutter 219s is moved, and the lower end opening of the manifold 209 is sealed by the shutter 219s via the O-ring 220c (shutter close). After being carried out to the outside of the reaction tube 203, the processed wafers 200 are taken out of the boat 217 (wafer discharge).
• the formation of the initial layer can be omitted, and in the case where the formation of the initial layer is omitted, by using a substance as the etching agent that is more reactive with the first film than with the second film and the third film, it becomes possible to effectively selectively remove the first film among the first film, the second film, and the third film.
• the above-mentioned abnormal growth refers to, for example, the film to be formed on the wafer 200 growing in a droplet (island) shape due to the influence of the surface state of the first film that is part of the base for the film formation process, i.e., the influence of OH (hydroxyl group) termination on the surface of the O-containing film.
• Abnormal growth may reduce the in-plane film thickness uniformity of the film to be formed on the wafer 200.
• Abnormal growth may also deteriorate the surface roughness (flatness) of the film to be formed on the wafer 200.
• Abnormal growth may also be a cause of particle generation in the processing chamber 201.
• a fourth film having a higher density than the third film can be laminated on the third film, and the low-density third film can be reinforced by the high-density fourth film. This makes it possible to increase the strength of the entire laminated film of the third film and the fourth film.
• the first reactant is an amine or an organic hydrazine
• the second reactant is hydrogen nitride
• the etching agent contains fluorine and hydrogen
• the first film can be etched with high selectivity while suppressing etching of the second film and the third film, and the accuracy of forming the air gap can be further improved.
• the etching agent may be a gaseous substance, a liquid substance, or may contain both.
• the etching agent may be, for example, an aqueous solution containing fluorine and hydrogen. When the etching agent is an aqueous solution, it is possible to etch the first film at a high etching rate, without leaving any residue, and with high selectivity.
• the initial layer formation, third film formation, etching, and fourth film formation can be performed in a non-plasma atmosphere, making it possible to prevent plasma damage to the wafer 200, etc.
• the first film and the second film are alternately arranged on the flat surface of the wafer, parallel to the surface.
• the substrate to be processed may be a wafer having a surface on which a plurality of recesses such as trenches are formed at predetermined intervals, and on which a first film formed to fill each recess and a second film formed outside the recesses are alternately arranged.
• the amount of the first film removed i.e., the size of the air gap
• the amount of the first film removed can be adjusted as desired by appropriately selecting the etching process conditions within the range of process conditions described above.
• the entire first film may be removed from within the recess formed on the surface of the wafer, or, for example, as shown in FIG. 6(d), a portion of the first film may be left in the recess formed on the surface of the wafer.
• the present disclosure is not limited to such an embodiment, and the initial layer may not be formed before the third film is formed.
• a treatment hydrophobization treatment
• a plasma treatment, an annealing treatment, a nitriding treatment (plasma nitriding treatment, thermal nitriding treatment), etc. can be performed. In this way, the surfaces of the first film and the second film can be made non-hydrophilic (hydrophobic) without forming the initial layer.
• the present disclosure is not limited to such an embodiment.
• the third film formed on the substrate may be heat-treated at a temperature in the range of 400 to 600°C, for example. This makes it possible to further increase the hardness of the third film.
• the heat treatment may be performed using the same processing procedure and conditions as PT.
• a series of steps from the formation of the initial layer to the formation of the fourth film are performed (in-situ) in the same processing chamber 201 of the substrate processing system.
• the present disclosure is not limited to such an embodiment.
• a specific step among the series of steps, such as PT or etching may be performed (ex-situ) in another processing chamber of the substrate processing system.
• a substrate processing system including a plurality of stand-alone substrate processing apparatuses first substrate processing apparatus, second substrate processing apparatus, third substrate processing apparatus, etc.
• a substrate processing system including a cluster-type substrate processing apparatus in which a plurality of processing chambers (first processing chamber, second processing chamber, third processing chamber, etc.) are provided around a transfer chamber may be used to perform each step in a different processing chamber of the same substrate processing apparatus, i.e., in a different processing unit.
• a substrate processing system including a cluster-type substrate processing apparatus in which a plurality of processing chambers (first processing chamber, second processing chamber, third processing chamber, etc.) are provided around a transfer chamber may be used to perform each step in a different processing chamber of the same substrate processing apparatus, i.e., in a different processing unit.
• the second film is a film containing a semiconductor element and nitrogen.
• the present disclosure is not limited to such an embodiment.
• the same effect as the above-mentioned embodiment can be obtained even if the second film is a film containing a metal element such as aluminum (Al), titanium (Ti), hafnium (Hf), zirconium (Zr), tantalum (Ta), molybdenum (Mo), copper (Cu), cobalt (Co), tungsten (W), or ruthenium (Ru).
• a metal element such as aluminum (Al), titanium (Ti), hafnium (Hf), zirconium (Zr), tantalum (Ta), molybdenum (Mo), copper (Cu), cobalt (Co), tungsten (W), or ruthenium (Ru).
• the third film is mainly a SiN film or a SiCN film.
• the present disclosure is not limited to such an embodiment.
• the third film is a film containing a semiconductor element such as a SiOC film, a SiOCN film, a SiON film, or a Si film, the same effect as the above-mentioned embodiment can be obtained.
• the fourth film is mainly a SiN film or a SiCN film.
• the present disclosure is not limited to such an embodiment.
• the fourth film is a film containing a semiconductor element such as a SiO film, a SiOC film, a SiOCN film, a SiON film, or a Si film, the same effect as the above-mentioned embodiment can be obtained.
• the recipes used for each process are preferably prepared individually according to the process content, and recorded and stored in the storage device 121c via an electric communication line or the external storage device 123. Then, when starting each process, the CPU 121a preferably selects an appropriate recipe from the multiple recipes recorded and stored in the storage device 121c according to the process content. This makes it possible to reproducibly form films of various film types, composition ratios, film qualities, and thicknesses using a single substrate processing device. It also reduces the burden on the operator, and allows each process to be started quickly while avoiding operating errors.
• the above-mentioned recipes do not necessarily have to be created anew, but may be prepared, for example, by modifying an existing recipe that has already been installed in the substrate processing apparatus.
• the modified recipe may be installed in the substrate processing apparatus via an electric communication line or a recording medium on which the recipe is recorded.
• an existing recipe that has already been installed in the substrate processing apparatus may be directly modified by operating the input/output device 122 provided in the existing substrate processing apparatus.
• an example of forming a film using a batch-type substrate processing apparatus that processes 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 to a case where a film is formed using a substrate processing apparatus having a cold-wall type processing furnace.
• 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.
• the process sequence described above was used to form an air gap on the surface of the substrate, and TEM images of the wafer surface during the formation process were taken.
• a Si wafer was prepared as a substrate to be processed, in which a first film ( 1st film) formed to fill the recesses and a second film ( 2nd film) formed outside the recesses were alternately arranged adjacent to each other.
• Fig. 7(a) shows a TEM image of the surface of the wafer in this example.
• FIG. 7 (b) shows a TEM image of the surface of the wafer in the example after the third film was formed. As shown in this TEM image, it can be seen that the third film is continuously formed on the first film and the second film.
• FIGS. 7(c) to 7(e) show TEM images of the surface of the wafer in the embodiment after etching, in order, when the etching agent exposure time was 30 minutes, 60 minutes, and 90 minutes. These images show that by performing etching, the first film can be selectively removed while retaining the second and third films, and an air gap can be formed on the wafer with high precision. It can also be seen that the amount of the first film removed, i.e., the size of the air gap, can be freely controlled by appropriately selecting the etching processing conditions (exposure time) from within the range of processing conditions for the etching in the above embodiment.
• FIGS. 7(f) and 7(g) show TEM images of the surface of the wafer in the example after etching was performed with an exposure time of the etching agent of 25 minutes, forming an air gap, and then forming the fourth film on the third film.
• Figure 7(f) is a partially enlarged TEM image of Figure 7(g). From these TEM images, it can be seen that a plurality of air gaps can be precisely formed on the wafer with high accuracy.

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