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
  • 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
• • 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
  • C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
• • 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
• • 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
  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/24—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using chemical vapour deposition [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
• • 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
  • H10P14/65—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials
  • H10P14/6502—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed before formation of the materials
  • H10P14/6512—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed before formation of the materials by exposure to a gas or vapour
• • 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
  • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
  • H10P14/6921—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon
  • H10P14/69215—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material being a silicon oxide, e.g. SiO2
• • 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

Definitions

• the present disclosure relates to a substrate processing method, a semiconductor device manufacturing method, a substrate processing apparatus, and a program.
• a process of forming a film on a substrate is sometimes performed (for example, see JP-A-2013-077805 and JP-A-2018-137356).
• the present disclosure provides a technique that can improve step coverage of a film formed on a substrate.
• a second raw material that is chemically more stable than the first raw material is generated, and the first raw material and the second raw material are combined.
• forming a first layer by exposing and adsorbing it to the surface of the substrate;
• a technique is provided for forming a film on the substrate by performing a cycle including a predetermined number of times.
• FIG. 1 is a schematic configuration diagram of a vertical processing furnace of a substrate processing apparatus that is preferably used in one embodiment of the present disclosure, and is a diagram showing a portion of a processing furnace 202 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 in FIG. 1 showing the processing furnace 202 portion.
• FIG. 3 is a schematic configuration diagram of a controller 121 of a substrate processing apparatus suitably used in one aspect of the present disclosure, and is a block diagram showing a control system of the controller 121.
• FIGS. 1 to 3 One aspect of the present disclosure will be described below, mainly with reference to FIGS. 1 to 3. 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 temperature regulator (heating section).
• 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 (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 (SiO 2 ) or silicon carbide (SiC), and has a cylindrical shape with a closed upper end and an open lower end.
• a manifold 209 is arranged 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 is performed on the wafer 200 within this processing chamber 201 .
• 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 nozzles 249a to 249c are different nozzles, and each of the nozzles 249a and 249c is provided adjacent to the nozzle 249b.
• the gas supply pipes 232a to 232c are provided with mass flow controllers (MFC) 241a to 241c, which are flow rate controllers (flow rate control units), and valves 243a to 243c, which are on-off valves, respectively, in order from the upstream side of the gas flow.
• MFC mass flow controllers
• a gas supply pipe 232d is connected to the gas supply pipe 232a downstream of the valve 243a.
• a gas supply pipe 232e is connected to the gas supply pipe 232b downstream of the valve 243b.
• a gas supply pipe 232f is connected to the gas supply pipe 232c downstream of the valve 243c.
• the gas supply pipes 232d to 232f are provided with MFCs 241d to 241f and valves 243d to 243f, respectively, in order from the upstream side of the gas flow.
• the gas supply pipes 232a to 232f are made of a metal material such as SUS, for example.
• 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 upper and lower portions of the inner wall of the reaction tube 203. They are each provided so as to rise upward in the arrangement direction. 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. In plan view, the nozzle 249b is arranged to face an exhaust port 231a, which will be described later, in a straight line across the center of the wafer 200 carried into the processing chamber 201.
• the nozzles 249a and 249c are arranged so that a straight line L passing through the nozzle 249b and the center of the exhaust port 231a is sandwiched from both sides along the inner wall of the reaction tube 203 (the outer circumference of the wafer 200).
• the straight line L is also a straight line passing through the nozzle 249b and the center of the wafer 200.
• the nozzle 249c can be said to be provided on the opposite side of the nozzle 249a with the straight line L interposed therebetween.
• the nozzles 249a and 249c are arranged symmetrically with respect to the straight line L as an axis of symmetry.
• Gas supply holes 250a to 250c for supplying gas are provided on the side surfaces of the nozzles 249a to 249c, respectively. Each of the gas supply holes 250a to 250c opens so as to face the exhaust port 231a in a plan view, and can supply gas toward the wafer 200. A plurality of gas supply holes 250a to 250c are provided from the bottom to the top of the reaction tube 203.
• the first raw material 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 additive is supplied from the gas supply pipe 232b into the processing chamber 201 via the MFC 241b, the valve 243b, and the nozzle 249b.
• a reactant is supplied from the gas supply pipe 232c into the processing chamber 201 via the MFC 241c, the valve 243c, and the nozzle 249c.
• Inert gas is supplied from the gas supply pipes 232d to 232f into the processing chamber 201 via MFCs 241d to 241f, valves 243d to 243f, gas supply pipes 232a to 232c, and nozzles 249a to 249c, respectively.
• the inert gas acts as a purge gas, carrier gas, diluent gas, etc.
• a first raw material supply system is mainly composed of the gas supply pipe 232a, MFC 241a, and valve 243a.
• the additive supply system is mainly composed of the gas supply pipe 232b, MFC 241b, and valve 243b.
• a reactant supply system is mainly composed of the gas supply pipe 232c, MFC 241c, and valve 243c.
• An inert gas supply system is mainly composed of gas supply pipes 232d to 232f, MFCs 241d to 241f, and valves 243d to 243f.
• any or all of the various supply systems described above may be configured as an integrated supply system 248 in which valves 243a to 243f, MFCs 241a to 241f, etc. are integrated.
• the integrated supply system 248 is connected to each of the gas supply pipes 232a to 232f, and performs operations for supplying various substances (various gases) into the gas supply pipes 232a to 232f, that is, opening and closing operations of the valves 243a to 243f.
• the flow rate adjustment operations and the like by the MFCs 241a to 241f are configured to be controlled by a controller 121, which will be described later.
• the integrated supply system 248 is configured as an integrated or divided 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. 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. As shown in FIG. 2, the exhaust port 231a is provided at a position that faces (faces) the nozzles 249a to 249c (gas supply holes 250a to 250c) with the wafer 200 in between when viewed from above.
• 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 in operation, and further, with the vacuum pump 246 in operation, 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.
• a 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 passes through the seal cap 219 and is connected to the boat 217.
• 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 serving as a substrate support is configured to support 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. They are arranged so that they are spaced apart.
• 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.
• 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 substrate processing apparatus, a process recipe in which procedures and conditions for substrate processing, etc., which will be described later, are described are recorded and stored in a readable manner.
• a process recipe is a combination of steps such that the controller 121 causes the substrate processing apparatus to execute each procedure in substrate processing 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 241f, valves 243a to 243f, 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 rates of various substances (various gases) by the MFCs 241a to 241f, opens and closes the valves 243a to 243f, opens and closes the APC valve 244, and adjusts the APC valve based on the pressure sensor 245 in accordance with the content of the read recipe.
• the shutter opening/closing mechanism 115s is configured to be able to control the opening/closing operation of the shutter 219s.
• 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 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 method of processing a substrate as one step of a semiconductor device manufacturing process (manufacturing method) using the above-mentioned substrate processing apparatus, that is, a process for forming a film on the wafer 200 as a substrate. An example of a sequence will be explained. In the following description, the operation of each part constituting the substrate processing apparatus is controlled by a controller 121.
• wafer used in this specification may mean the wafer itself, or a laminate of the wafer and a predetermined layer or film formed on its surface.
• wafer surface used in this specification may mean the surface of the wafer itself or the surface of a predetermined layer formed on the wafer.
• forming a predetermined layer on a wafer refers to forming a predetermined layer directly on the surface of the wafer itself, or a layer formed on the wafer, etc. Sometimes it means forming a predetermined layer on top of.
• substrate when the word “substrate” is used, it has the same meaning as when the word "wafer” is used.
• agent used herein includes at least one of a gaseous substance and a liquid substance.
• Liquid substances include mist substances. That is, each of the additive, the oxidizing agent, and the nitriding agent may contain a gaseous substance, a liquid substance such as a mist-like substance, or both.
• both the first layer and the second layer may include a continuous layer, a discontinuous layer, or both.
• the wafers 200 loaded onto the boat 217 have a three-dimensional surface, that is, a surface that is not a flat surface, for example, a surface with recesses or steps formed by trenches, holes, or both.
• 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 based on the measured pressure information.
• the wafer 200 in the processing chamber 201 is heated by the heater 207 so that it reaches 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.
• rotation of the wafer 200 by the rotation mechanism 267 is started. Evacuation of the processing chamber 201, heating of the wafer 200, and rotation of the wafer 200 are all continued at least until the processing of the wafer 200 is completed.
• Step A After that, the first raw material and additives are supplied to the wafer 200.
• valves 243a and 243b are opened to flow the first raw material and additive into the gas supply pipes 232a and 232b, respectively.
• the flow rates of the first raw material and the additive are adjusted by the MFCs 241a and 241b, respectively, and are supplied into the processing chamber 201 through the nozzles 249a and 249b, mixed within the processing chamber 201, and exhausted from the exhaust port 231a.
• the first raw material and the additive are supplied to the wafer 200 from the side of the wafer 200 (first raw material + additive supply).
• the valves 243d to 243f may be opened to supply inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively.
• the processing conditions when supplying the first raw material and additives in step A are as follows: Processing temperature: 350-800°C, preferably 350-650°C Processing pressure: 1 to 1333 Pa, preferably 1 to 931 Pa First raw material supply flow rate: 0.01-5slm, 0.1-2slm Additive supply flow rate: 0.01-10slm, 0.1-5slm Inert gas supply flow rate (for each gas supply pipe): 0 to 10slm Each substance supply time: 1 to 120 seconds, preferably 1 to 60 seconds.
• 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.
• the processing time means the time during which the processing is continued. Further, when the supply flow rate includes 0 slm, 0 slm means a case in which the substance (gas) is not supplied. The same applies to the following description.
• a second raw material that is chemically more stable than the first raw material is generated, and the first raw material and the second raw material are combined.
• the surface of the wafer 200 can be exposed.
• the first raw material and the second raw material exposed to the surface of the wafer 200 are adsorbed to the surface of the wafer 200, and a first layer is formed on the surface of the wafer 200.
• the second raw material produced in this step is chemically more stable than the first raw material, so it is a compound that is less likely to decompose and cause less gas phase reactions (also referred to as CVD reactions) than the first raw material. You can say that. Therefore, when the first raw material and the second raw material are exposed to the surface of the wafer 200, they are not decomposed compared to when only the first raw material is exposed to the surface of the wafer 200 under the same processing conditions.
• the ratio of raw materials (first raw material, second raw material) in a state where gas phase reactions have not occurred (undecomposed) and which have not undergone a gas phase reaction increases in the proportion that they contribute to the formation of the first layer.
• Undecomposed raw materials (first raw material, second raw material) in a state where a gas phase reaction has not occurred are easily supplied to various parts within the recess of the wafer 200, so the thickness of the bottom and the top of the recess are different.
• a first layer is formed with a small difference in . Since such a first layer is formed in step A, the step coverage of the film formed on the surface of the wafer 200 can be improved by performing a cycle including step A and step B a predetermined number of times. It becomes possible.
• “improving the step coverage of the film formed on the surface of the wafer 200" will also be simply referred to as “improving the step coverage.”
• a part of the first raw material is reacted with the additive to change the first bond contained in the part of the first raw material into a second bond having a higher bond energy. It is preferable to convert a part of one raw material into a second raw material. By doing so, it becomes possible to generate a second raw material that is chemically more stable than the first raw material from the first raw material, and the effect of improving step coverage can be sufficiently obtained.
• the bond with the lowest bond energy contained in the second raw material has a higher bond energy than the bond with the lowest bond energy contained in the first raw material.
• the chemical stability of the second raw material can be made higher than the chemical stability of the first raw material, and the effect of improving step coverage can be sufficiently obtained.
• a part of the first raw material is decomposed to generate an intermediate, and the intermediate and the additive are reacted, so that the first raw material is lower than the first raw material, or the intermediate and the first raw material are each lower than the first raw material.
• a part of the first raw material is changed into the second raw material by changing the first bond contained in a part of the first raw material to a second bond having a higher bond energy. Good too.
• the bond having the lowest bond energy contained in the generated second raw material may have a higher bond energy than the bond having the lowest bond energy contained in the first raw material.
• the activation energy required for the reaction with the second layer which will be described later, in the generated second raw material is greater than or equal to the activation energy required for the reaction with the second layer in the first raw material, and
• the activation energy required for the reaction of one raw material with the second layer is higher than the activation energy required for the reaction of the intermediate produced by decomposing the first raw material with the second layer. is preferred.
• the reactivity of the second raw material with the second layer can be made lower than the reactivity of the first raw material with the second layer, and the reactivity of the first raw material with the second layer can be made lower than the reactivity of the first raw material with the second layer.
• the raw materials can be easily supplied to various parts of the wafer 200, and for example, can easily reach the bottom of the recess of the wafer 200, which also has the effect of improving step coverage. You will get enough.
• the first layer is formed by exposing the first raw material and the second raw material generated from a part of the first raw material to the surface of the wafer 200 and adsorbing them.
• the sum of the amount of exposure of the first raw material and the amount of exposure of the second raw material to the surface of the wafer 200 can be set to be greater than or equal to the amount of exposure of the decomposed first raw material to the surface of the wafer 200.
• the sum of the amount of exposure of the first raw material and the amount of exposure of the second raw material to the surface of the wafer 200 is more preferably greater than the amount of exposure of the decomposed first raw material to the surface of the wafer 200.
• the exposure amounts of the first raw material and the second raw material can be significantly obtained.
• first raw material and second raw material are simply used to represent a substance, it means that the substance is in an undecomposed state.
• a term such as “decomposed first raw material” is used to represent a substance, it means that the substance is in a decomposed state. Therefore, the "decomposed first raw material” includes an intermediate produced by decomposing the first raw material described above.
• the sum of the amount of the first raw material adsorbed onto the surface of the wafer 200 and the amount of the second raw material adsorbed onto the surface of the wafer 200 is greater than or equal to the amount of adsorption of the decomposed first raw material onto the surface of the wafer 200. It is more preferable that the total amount of the first raw material adsorbed on the surface of the wafer 200 and the amount of the second raw material adsorbed is larger than the amount of the decomposed first raw material adsorbed on the surface of the wafer 200 .
• the adsorption amount of the first raw material and the adsorption amount of the second raw material are determined based on the sum of the adsorption amount of the first raw material, the adsorption amount of the second raw material, and the adsorption amount of the decomposed first raw material on the surface of the wafer 200. It is preferable that the total proportion of the above-mentioned elements is 50% or more, more preferably 60% or more, and still more preferably 70% or more.
• the amount of adsorption of the first raw material and the amount of adsorption of the second raw material relative to the sum of the amount of adsorption of the first raw material, the amount of adsorption of the second raw material, and the amount of adsorption of the decomposed first raw material on the surface of the wafer 200 is The total percentage is preferably 95% or less, more preferably 90% or less, and even more preferably 80% or less.
• the adsorption amount of the first raw material and the adsorption amount of the second raw material are determined relative to the sum of the adsorption amount of the first raw material, the adsorption amount of the second raw material, and the adsorption amount of the decomposed first raw material on the surface of the wafer 200. If the total ratio is less than 50%, the amount of decomposition of the first raw material becomes excessive, and step coverage may deteriorate. By setting this ratio to 50% or more, decomposition of the first raw material can be suppressed, the amount of decomposition of the first raw material can be reduced, and step coverage can be increased.
• Step A the adsorption amount of the first raw material and the adsorption amount of the decomposed first raw material are determined on the surface of the wafer 200 with respect to the sum of the adsorption amount of the first raw material, the adsorption amount of the second raw material, and the adsorption amount of the decomposed first raw material.
• the total ratio of the adsorption amount of the two raw materials is preferably 50% or more, more preferably 60% or more, and still more preferably 70% or more.
• the adsorption amount of the first raw material and the adsorption amount of the second raw material are determined relative to the sum of the adsorption amount of the first raw material, the adsorption amount of the second raw material, and the adsorption amount of the decomposed first raw material on the surface of the wafer 200. If the total ratio with the adsorption amount is higher than 95%, the film formation rate may decrease and productivity may deteriorate. By setting this ratio to 95% or less, it is possible to suppress a decrease in the film formation rate and increase productivity. By setting this ratio to 90% or less, it is possible to further suppress a decrease in the film formation rate, and it is possible to further increase productivity.
• Step A the ratio of the adsorption amount of the first raw material to the total of the adsorption amount of the first raw material, the adsorption amount of the second raw material, and the adsorption amount of the decomposed first raw material on the surface of the wafer 200 is determined. is preferably 95% or less, more preferably 90% or less, and even more preferably 80% or less.
• the exposure amount (adsorption amount) of the second raw material to the surface of the wafer 200 is divided into the exposure amount (adsorption amount) of the first raw material to the surface of the wafer 200 and the exposure amount of the first raw material.
• (adsorption amount) and the amount of exposure of the second raw material to the surface of the wafer 200 (amount of adsorption) is the amount of exposure of the first raw material to the surface of the wafer 200 (amount of adsorption).
• the amount may be greater than the total of the amount of exposure (adsorption amount) of the decomposed first raw material.
• the exposure amount (adsorption amount) of the first raw material to the surface of the wafer 200 is decomposed into the exposure amount (adsorption amount) of the second raw material to the surface of the wafer 200.
• (adsorption amount) and the amount of exposure of the first raw material to the surface of the wafer 200 is the amount of exposure of the second raw material to the surface of the wafer 200 and the amount of exposure of the decomposed first raw material. The amount may be greater than the total amount.
• the valves 243a and 243b are closed to stop the supply of the first raw material and the additive into the processing chamber 201, respectively. Then, the inside of the processing chamber 201 is evacuated to remove gaseous substances remaining inside the processing chamber 201 from the inside of the processing chamber 201 . At this time, the valves 243d to 243f are opened to supply inert gas into the processing chamber 201 through the nozzles 249a to 249c. The inert gas supplied from the nozzles 249a to 249c acts as a purge gas, thereby purging the inside of the processing chamber 201 (purge).
• the processing conditions when purging in step A are as follows: Processing pressure: 1-30Pa Processing time: 1 to 120 seconds, preferably 1 to 60 seconds Inert gas supply flow rate (per gas supply pipe): 0.5 to 20 slm is exemplified. Note that the processing temperature when purging is performed in this step is preferably the same temperature as the processing temperature when supplying the first raw material and additives.
• first raw material for example, a compound containing a main element (main component) constituting the film formed on the wafer 200 and a halogen can be used.
• the compound containing the main element constituting the film and halogen for example, halosilane containing silicon (Si) and halogen can be used.
• halosilane means a silane having a halogen element as a substituent.
• the halogen element contained in the halosilane include chlorine (Cl), fluorine (F), bromine (Br), and iodine (I), with Cl, Br, and I being preferred, and Cl being more preferred.
• halosilanes it is more preferable to use chlorosilanes.
• a halosilane containing one Si in one molecule may be used, or a halosilane containing two or more (preferably two) Si in one molecule may be used.
• a halosilane containing at least one of a Si--Si bond and a Si--hydrogen (H) bond in one molecule it is preferable to use a halosilane containing at least one of a Si--Si bond and a Si--hydrogen (H) bond in one molecule.
• the first raw material examples include chlorosilane gases having Si--H bonds such as monochlorosilane (SiH 3 Cl) gas, dichlorosilane (SiH 2 Cl 2 ) gas, and trichlorosilane (SiHCl 3 ) gas, and hexachlorodisilane (A chlorosilane gas having an Si--Si bond, such as Si 2 Cl 6 ) gas, can be used.
• a bromosilane-based gas having an Si--H bond such as monobromosilane (SiH 3 Br) gas, dibromosilane (SiH 2 Br 2 ) gas, tribromosilane (SiHBr 3 ) gas, etc.
• an alkylhalosilane containing Si, a halogen, and an alkyl group can be used as the first raw material.
• the alkylhalosilane gas include 1,1,2,2-tetrachloro-1,2-dimethyldisilane ((CH 3 ) 2 Si 2 Cl 4 ) gas, 1,2-dichloro-1,1,
• An alkylchlorosilane gas having a Si--Si bond such as 2,2-tetramethyldisilane ((CH 3 ) 4 Si 2 Cl 2 ) gas can be used.
• an alkylchlorosilane gas having a Si--H bond such as dimethylchlorosilane ((CH 3 ) 2 SiHCl) can be used.
• an alkylchlorosilane gas having a Si--H bond such as dimethylchlorosilane ((CH 3 ) 2 SiHCl) can be used.
• a Si--H bond such as dimethylchlorosilane ((CH 3 ) 2 SiHCl)
• a Si--H bond such as dimethylchlorosilane ((CH 3 ) 2 SiHCl)
• a compound containing the main element constituting the film formed on the wafer 200 and an amino group can also be used.
• the compound containing the main element constituting the film and an amino group for example, aminosilane containing Si and an amino group can be used.
• Aminosilane means a silane having an amino group as a substituent.
• the amino group contained in the aminosilane may be either an unsubstituted amino group or a substituted amino group.
• the substituted amino group for example, a substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms or a substituted amino group substituted with SiH 3 can be used.
• the two substituents of the substituted amino group may be the same or different.
• aminosilane in addition to Si-N bonds, in which Si and nitrogen (N) constituting the amino group are bonded, Si-H bonds, in which Si and H are bonded, and Si and oxygen (O) are bonded. It is preferable to further contain at least one of Si—O bonds. It is also preferable that the aminosilane contains an Si--N bond, at least one of an Si--H bond and a Si--O bond, and an Si--C bond in which Si and carbon (C) are bonded.
• aminosilane for example, Si--H bonds such as diisopropylaminosilane (SiH 3 [N(C 3 H 7 ) 2 ]) gas and di-secandabutylaminosilane (SiH 3 [H(C 4 H 9 ) 2 ]) gas are used.
• An aminosilane gas having three aminosilanes in its molecule can be used.
• aminosilane examples include bis(diethylamino)silane (SiH 2 [N(C 3 H 7 ) 2 ] 2 ) gas, bis(dipropylamino) silane (SiH 2 [N(C 3 H 7 ) 2 ] 2 )
• An aminosilane gas having two Si--H bonds in its molecule such as a gas
• an aminosilane gas having one Si--H bond in the molecule such as tris(dimethylamino)silane (SiH[N(CH 3 ) 2 ] 3 ), can be used.
• One or more of these can be used as the first raw material.
• a compound containing a main element constituting the film formed on the wafer 200 and an alkoxy group can also be used.
• the compound containing the main element constituting the film and an alkoxy group for example, an alkoxysilane containing Si and an alkoxy group can be used.
• Alkoxysilane means a silane having an alkoxy group as a substituent. Alkoxysilane has properties of being chemically stable and thermally stable, and by using this compound, step coverage can be further improved.
• the alkoxy group for example, an alkoxy group having 1 to 4 carbon atoms can be used.
• the alkoxysilane is preferably an alkoxyaminosilane further containing an amino group as a substituent.
• the alkoxysilane is an alkoxyaminosilane containing an Si--O bond in which Si and O constituting the alkoxy group are bonded, as well as an Si-N bond in which Si and N constituting the alkoxy group are bonded. preferable.
• Alkoxyaminosilane for example, is a compound that can achieve both adsorption to the wafer 200 and chemical and thermal stability, and by using this compound, it is possible to further improve step coverage. It is.
• the number of alkoxy groups in one molecule is preferably greater than the number of amino groups, preferably greater than the number of amino groups.
• the number of chemical bonds between Si and an alkoxy group i.e., the number of Si--O bonds
• alkoxyaminosilane for example, an alkoxyaminosilane gas having three Si-O bonds in the molecule, such as (dimethylamino)trimethoxysilane (Si(OCH 3 ) 3 [N(CH 3 ) 2 ]) gas, is used. be able to.
• alkoxyaminosilanes include alkoxyaminosilane gases having two Si-O bonds in the molecule, such as bis(dimethylamino)dimethoxysilane (Si(OCH 3 ) 2 [N(CH 3 ) 2 ] 2 ) gas. Can be used.
• an alkoxyaminosilane gas having one Si-O bond in the molecule such as tris(dimethylamino)methoxysilane (Si(OCH 3 ) [N(CH 3 ) 2 ] 3 ) gas, is used. be able to. One or more of these can be used as the first raw material.
• silylamine can also be used.
• silylamine for example, a silylamine gas having three Si--N bonds in the molecule, such as trisilylamine (N(SiH 3 ) 3 ) gas, can be used.
• additive for example, simple halogen, hydrogen halide, hydrocarbon, halogenated hydrocarbon, halogenated carbon, hydrogen (H 2 ), hydrogen nitride, and alcohol can be used.
• halogen for example, fluorine (F 2 ), chlorine (Cl 2 ), and bromine (Br 2 )
• hydrogen halide for example, hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), and hydrogen iodide (HI)
• hydrocarbons include saturated hydrocarbons such as methane (CH 4 ), ethane (C 2 H 6 ), propane (C 3 H 8 ), butane (C 4 H 10 ), ethylene (C 2 H 4 ), Unsaturated hydrocarbons such as propylene (C 3 H 6 ) and butene (C 4 H 8 ) can be used.
• halogenated hydrocarbons examples include trifluoromethane (CHF 3 ), difluoromethane (CH 2 F 2 ), fluoromethane (CH 3 F), trichloromethane (CHCl 3 ), dichloromethane (CH 2 Cl 2 ), and chloromethane.
• CH 3 Cl can be used.
• the halogenated carbon carbon tetrafluoride (CF 4 ) and carbon tetrachloride (CCl 4 ) can be used, for example.
• hydrogen nitride for example, ammonia (NH 3 ) can be used.
• the alcohol for example, methanol (CH 3 OH), ethanol (C 2 H 5 OH), and propanol (C 3 H 7 OH) can be used.
• the additive one or more of these 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 can be used.
• nitrogen (N 2 ) gas argon (Ar) gas, helium (He) gas, neon (Ne) gas, or xenon (Xe) gas
• argon (Ar) gas argon (Ar) gas
• He helium
• Ne neon
• Xe xenon
• Schemes (1) and (2) respectively show a first embodiment using a first raw material that is a compound containing Si and a halogen (e.g., halosilane, alkylhalosilane), and a compound containing Si and an amino group. (for example, aminosilane, alkoxyaminosilane, silylamine).
• the second aspect further includes an aspect (2-1 aspect) in which the first raw material is a compound containing Si and an amino group and has an Si--H bond, and an aspect in which the first raw material is a compound containing Si and an amino group and has an Si--H bond.
• an embodiment (2-2 embodiment) in which the first raw material is a compound containing Si-H bonds and does not have an Si--H bond.
• A represents a halogen atom or an alkyl group
• B represents a hydrogen atom (H)
• Z represents an elemental halogen, a hydrogen halide, or a hydrocarbon.
• Z' represents a group containing a part of the molecule of Z
• B' represents a product generated by cutting the Si--B bond, or a product of the molecule of B.
• at least one of A represents a halogen atom.
• the plural A's may be different from each other or may be all the same.
• the plurality of Z's may be different from each other or may be all the same.
• the first raw material used in the first embodiment has a Si-H bond as a Si-B bond.
• Si--H bonds have lower bond energy than other chemical bonds (eg, Si-halogen bonds, etc.).
• the Si-H bond has the property of being more easily broken than other chemical bonds (eg, Si-halogen bond, etc.) under the above-mentioned processing conditions.
• the Si-Z' bonds (e.g., Si-N bonds, Si-halogen bonds, Si-C bonds, etc.) in the second raw material produced as described above have a lower bond energy than the Si-H bonds in the first raw material. becomes high.
• a part of the first raw material and the additive are reacted to make the first bond (here, Si-H bond) contained in the part of the first raw material more
• a part of the first raw material can be converted into a second raw material. change to This makes it possible to produce a second raw material that is more chemically stable than the first raw material.
• Si--H bonds in the first raw material may be changed to Si--Z' bonds, or all of them may be changed to Si--Z' bonds. That is, the second raw material may have Si--H bonds (Si--H bonds may remain) or may not have Si--H bonds.
• the processing temperature is 400 to 800°C.
• A represents an amino group, an alkyl group, or an alkoxy group
• B represents a hydrogen atom
• Z represents hydrogen, hydrogen nitride, alcohol
• It represents a hydrocarbon, a halogenated hydrocarbon, or a halogenated carbon
• Z' represents a group containing a part of the molecule of Z
• B' represents a product produced by cutting the Si-B bond, or a product of B.
• at least one of A represents an amino group.
• the amino group represented by A may be either an unsubstituted amino group or a substituted amino group, and a substituted amino group is particularly preferred.
• a substituted amino group for example, a substituted amino group substituted with an alkyl group having 1 to 4 carbon atoms or a substituted amino group substituted with SiH 3 can be used.
• the plural A's may be different from each other or may be all the same.
• the plurality of Z's may be different from each other or may be all the same.
• the first raw material used in the 2-1st embodiment has a Si-H bond as a Si-B bond.
• Si--H bonds have lower bond energy than other chemical bonds (eg, Si--N bonds, Si--O bonds, etc.).
• Si--H bonds have the property of being more easily broken than other chemical bonds (eg, Si--N bonds, Si--O bonds, etc.) under the above-mentioned processing conditions.
• the Si-Z' bonds (e.g., Si-N bonds, Si-halogen bonds, Si-C bonds, etc.) in the second raw material produced as described above have a lower bond energy than the Si-H bonds in the first raw material. becomes high.
• the first bond here, Si-H bond
• the first bond contained in a part of the first raw material
• a second bond here, a Si-N bond as a Si-Z' bond, a Si-halogen bond, a Si-C bond, etc.
• the Si--H bonds that the first raw material has may change to Si--Z' bonds, or all of them may change to Si--Z' bonds.
• the second raw material may have Si--H bonds (Si--H bonds may remain) or may not have Si--H bonds.
• A may be a substituted amino group substituted with an alkyl group (for example, a dimethylamino group, a diethylamino group, a dipropylamino group, etc.).
• A which is a substituted amino group substituted with an alkyl group, may react with additive Z (for example, NH 3 ) to form an unsubstituted amino group (-NH 2 ). It may change. That is, in this case, A, which was a substituted amino group substituted with an alkyl group in the first raw material, becomes an unsubstituted amino group (-NH 2 ) in the second raw material.
• the N--H bond of an unsubstituted amino group has higher bond energy than the N--C bond of an amino group substituted with an alkyl group. Therefore, when the above change occurs in A, it is possible to produce a second raw material that is chemically more stable than the first raw material, compared to a case where there is no such change.
• the processing temperature is preferably 400 to 700°C.
• A represents an alkyl group or an alkoxy group
• B represents an amino group
• Z represents hydrogen nitride
• alcohol, hydrocarbon, halogen represents a hydrogenated hydrocarbon or a halogenated carbon
• Z' represents a group containing a part of the molecule of Z
• B' represents a product generated by cutting the Si-B bond
• At least one of B is a substituted amino group substituted with an alkyl group (eg, dimethylamino group, diethylamino group, dipropylamino group, etc.).
• an alkyl group eg, dimethylamino group, diethylamino group, dipropylamino group, etc.
• the plurality of Z's may be different from each other or may be all the same.
• the first raw material used in the 2-2 embodiment has a substituted amino group substituted with an alkyl group in B.
• the N-C bond possessed by the substituted amino group substituted with an alkyl group has a higher bond energy than other chemical bonds (e.g., Si-O bond, Si-C bond, O-C bond, C-H bond, etc.). low.
• the first raw material B having an NC bond with a lower bond energy reacts with the additive Z, and the bond energy is higher than that of the NC bond.
• a second raw material having Z' containing a bond (eg, an N--H bond, etc.) is produced.
• the bonds contained in Z' in the second raw material produced as described above have a lower bond energy than the bonds contained in B in the first raw material (for example, N-C bond). becomes high.
• the first bond (here, the NC bond) contained in the part of the first raw material is A part of the first raw material is changed into a second raw material by changing it to a second bond (here, an N--H bond, etc.) having a higher bond energy.
• a second bond here, an N--H bond, etc.
• the processing temperature is preferably 450 to 800°C.
• the first raw material as illustrated in scheme (3) can be used. It becomes possible to generate a second raw material that is chemically more stable than the first raw material by causing a reaction with the additive.
• the first raw material as illustrated in scheme (4) below can be A reaction between an intermediate produced by partially decomposing the additive and an additive is caused to produce a second raw material that is chemically more stable than the first raw material or each of the intermediate and the first raw material. It becomes possible to do so. Note that in this step, the reaction shown in scheme (3) and the reaction shown in scheme (4) may occur simultaneously.
• A represents a halogen atom or an alkyl group
• Z represents a simple halogen, a hydrogen halide, a hydrocarbon, a halogenated hydrocarbon, or a halogenated carbon
• Z' represents a group containing a part of the molecule of Z.
• the plurality of Z's may be different from each other or may be all the same.
• the Si--Si bond in the first raw material represented by "A 3 Si--SiA 3 " has a lower bond energy than the Si--A bond (eg, Si-halogen bond, Si-C bond).
• the Si-Z' bonds (e.g., Si-halogen bonds, Si-H bonds, Si-C bonds, etc.) in the second raw material produced as described above have a lower bond energy than the Si-Si bonds in the first raw material. becomes high.
• the first bond here, Si-Si bond
• a part of the first raw material is changed into the second raw material by changing into 2 bonds (here, Si-halogen bond, Si-H bond, Si-C bond, etc.).
• the treatment temperature is preferably 350 to 800°C among the treatment conditions described above. By selecting such a treatment temperature, the reactions shown in schemes (3) and (4) above can be performed more efficiently.
• Step B After step A is completed, a reactant is supplied to the wafer 200, ie, the wafer 200 after the first layer has been formed.
• valve 243c is opened and the reactant is allowed to flow into the gas supply pipe 232c.
• the flow rate of the reactants is adjusted by the MFC 241c, and the reactants are supplied into the processing chamber 201 through the nozzle 249c, mixed within the processing chamber 201, and exhausted from the exhaust port 231a.
• a reactant is supplied to the wafer 200 from the side of the wafer 200 (reactant supply).
• the valves 243d to 243f may be opened to supply inert gas into the processing chamber 201 through the nozzles 249a to 249c, respectively.
• the processing conditions when supplying the reactants in step B are as follows: Processing temperature: 350-800°C, preferably 350-650°C Processing pressure: 1 to 4000 Pa, preferably 1 to 931 Pa Reactant supply flow rate: 1 to 20 slm, preferably 1 to 10 slm Inert gas supply flow rate (for each gas supply pipe): 0 to 10slm Each substance supply time: 1 to 120 seconds, preferably 1 to 60 seconds.
• the first layer By supplying reactants to the wafer 200 under the above-described processing conditions, it is possible to transform the first layer into the second layer. Specifically, in this step, by supplying a reactant to the wafer 200 under the above-mentioned processing conditions, the elements contained in the reactant are added to the first layer, and the elements contained in the reactant are added to the first layer. It becomes possible to change the composition. This makes it possible to change (convert) the first layer into a second layer having a composition different from that of the first layer.
• the valve 243c is closed and the supply of the reactant into the processing chamber 201 is stopped. Then, gaseous substances remaining in the processing chamber 201 are removed from the processing chamber 201 using the same processing procedure and processing conditions as in the purge in step A (purge). Note that the processing temperature when purging in this step is preferably the same as the processing temperature when supplying the reactant.
• an oxidizing agent for example, an O-containing gas or a H and O-containing gas can be used.
• the O-containing gas for example, oxygen (O 2 ) gas, ozone (O 3 ) gas, etc. can be used.
• the H and O-containing gas for example, water vapor (H 2 O gas), hydrogen peroxide (H 2 O 2 ) gas, H 2 gas + O 2 gas, H 2 gas + O 3 gas, etc. can be used. That is, as the H- and O-containing gas, H-containing gas + O-containing gas (reducing gas + oxidizing gas) can also be used.
• deuterium (D 2 ) gas may be used instead of H 2 gas as the H-containing gas, that is, the reducing gas.
• D 2 deuterium
• H 2 gas + O 2 gas means a mixed gas of H 2 gas and O 2 gas.
• the two gases may be mixed (premixed) in a supply pipe and then supplied into the processing chamber 201, or the two gases may be separately supplied to the processing chamber from different supply pipes.
• the components may be supplied into the processing chamber 201 and mixed (post-mixed) within the processing chamber 201.
• a nitriding agent can also be used.
• a gas containing N and H can be used.
• the N- and H-containing gas for example, 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 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 N- and H-containing gas for example, a C-, N-, and H-containing gas can be used.
• C, N and H containing gases examples include monoethylamine (C 2 H 5 NH 2 ) gas, diethylamine ((C 2 H 5 ) 2 NH) gas, triethylamine ((C 2 H 5 ) 3 N) gas, etc.
• ethylamine gas such as monomethylamine (CH 3 NH 2 ) gas, dimethylamine ((CH 3 ) 2 NH) gas, trimethylamine ((CH 3 ) 3 N) gas, monomethyl hydrazine (( Organic hydrazine gases such as CH 3 ) HN 2 H 2 ) gas, dimethylhydrazine ((CH 3 ) 2 N 2 H 2 ) gas, and trimethylhydrazine ((CH 3 ) 2 N 2 (CH 3 )H) gas, etc. Can be used. One or more of these can be used as the reactant.
• a C- and H-containing gas or a boron (B)-containing gas can also be used.
• a C- and H-containing gas for example, a hydrocarbon gas such as ethylene (C 2 H 4 ) gas, acetylene (C 2 H 2 ) gas, propylene (C 3 H 6 ) gas, etc. can be used.
• a B-containing gas for example, trichloroborane (BCl 3 ) gas, diborane (B 2 H 6 ) gas, triethylborane ((C 2 H 5 ) 3 B) gas, etc. can be used. One or more of these can be used as the reactant.
• n times an integer of 1 or 2 or more
• a desired pattern is formed on the surface of the wafer 200. It is possible to form (grow) a thick film.
• the above-described cycle is repeated multiple times. That is, the thickness of the second layer formed per cycle is made thinner than the desired thickness, and the above-mentioned process is continued until the thickness of the film formed by laminating the second layer reaches the desired thickness.
• the cycle is repeated multiple times.
• the surface of the wafer 200 can be coated with, for example, a silicon oxide film (SiO film), a silicon nitride film (SiN film), a silicon oxycarbonitride film, and a silicon oxycarbonitride film.
• SiO film silicon oxide film
• SiN film silicon nitride film
• Si oxycarbonitride film silicon oxycarbonitride film
• SiOCN film silicon oxycarbide film (SiOC film), silicon oxynitride film (SiON film), silicon carbonitride film (SiCN film), silicon carbide film (SiC film), silicon borocarbonitride film (SiBCN film) , silicon-containing films such as silicon boron nitride film (SiBN film), silicon boron carbide film (SiBC film), silicon boron carbonitride film (SiBOCN film), silicon boron oxynitride film (SiBON film), silicon borate carbonate film (SiBOC film), etc.
• a film can be formed.
• an inert gas as a purge gas is supplied into the processing 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 A a second raw material that is chemically more stable than the first raw material is generated, and the first raw material and the second raw material are exposed to the surface of the wafer 200 and adsorbed, thereby forming the first layer.
• the second raw material is chemically more stable than the first raw material, so compared to the case where only the first raw material is used, it is not decomposed (undecomposed) and no gas phase reaction occurs.
• the ratio of the raw materials (first raw material, second raw material) contributing to the formation of the first layer increases.
• the undecomposed raw materials (first raw material, second raw material) in a state where a gas phase reaction has not occurred are supplied to various locations within the recess of the wafer 200, and there is a difference in thickness between the bottom and top of the recess.
• a small first layer is formed.
• the first raw material contains a compound containing a main element constituting the film and a halogen
• the additive is one of halogen alone, hydrogen halide, hydrocarbon, halogenated hydrocarbon, and halogenated carbon. Combinations containing at least one of these are preferred.
• the first raw material and additive are used in this combination, it is possible to efficiently generate a second raw material that is more chemically stable than the first raw material. As a result, the effect of improving the step coverage of the film formed on the wafer 200 becomes more noticeable.
• the first raw material contains at least one of a compound containing a main element constituting the film and an amino group, a compound containing a main element constituting the film and an alkoxy group, and a silylamine, and
• the agent contains at least one of hydrogen, hydrogen nitride, alcohol, hydrocarbon, halogenated hydrocarbon, and halogenated carbon.
• step A it is preferable to use a compound containing an alkoxy group and the main element constituting the film, such as an alkoxysilane, as the first raw material, and it is preferable that such a compound further contains an amino group. That is, as the first raw material, it is preferable to use a compound containing a main element constituting the film, an alkoxy group, and an amino group, such as alkoxyaminosilane.
• the first raw material is a compound having such a structure, the effect of improving the step coverage of the film formed on the wafer 200 becomes more noticeable.
• the number of alkoxy groups in one molecule is preferably greater than or equal to the number of amino groups; More preferably, the number is greater than the number of groups.
• the number of chemical bonds between the atoms of the main element and the alkoxy group is preferably greater than or equal to the number of chemical bonds between the atoms of the main element and the amino group, and the number of chemical bonds between the atoms of the main element and the amino group is preferably greater than or equal to the number of chemical bonds between the atoms of the main element and the amino group. It is more preferable that the number is greater than .
• the first raw material is a compound having such a structure, the effect of improving the step coverage of the film formed on the wafer 200 becomes more noticeable.
• the substrate processing sequence in this embodiment can be modified as in the following modifications. Unless otherwise described, the processing procedure and processing conditions in each step of the modified example can be the same as the processing procedure and processing conditions in each step of the substrate processing sequence described above.
• step B may be a step of supplying different types of reactants (e.g., a first reactant, a second reactant, a third reactant shown below) non-simultaneously.
• n is an integer of 1 or more or an integer of 2 or more
• m is an integer of 1 or more or an integer of 2 or more.
• the first reactant, the second reactant, and the third reactant shown below are reactants having different molecular structures.
• any of the various reactants described above can be used.
• the main element constituting the film is not limited to Si.
• the main elements constituting the film include semiconductor elements such as germanium (Ge), titanium (Ti), tantalum (Ta), molybdenum (Mo), tungsten (W), ruthenium (Ru), Examples include metal elements such as aluminum (Al), zirconium (Zr), and hafnium (Hf).
• a film containing a semiconductor element such as Ge or a film containing a metal element such as Ti, Ta, Mo, W, Ru, Al, Zr, or Hf may be formed. becomes possible.
• the recipes used for each process be prepared individually according to the content of the process, and recorded and stored in the storage device 121c via a telecommunications line or the external storage device 123.
• the CPU 121a appropriately selects an appropriate recipe from among the plurality of recipes recorded and stored in the storage device 121c according to the process content. 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 being newly created, but may be prepared by, for example, modifying 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.
• the input/output device 122 provided in the existing substrate processing apparatus may be operated to directly change an existing recipe already installed in the substrate processing apparatus.
• a film is formed using a batch-type substrate processing apparatus that processes a plurality of substrates at once.
• the present disclosure is not limited to the above-described embodiments, and can be suitably applied, for example, to a case where a film is formed using a single-wafer type substrate processing apparatus that processes one or several substrates at a time.
• an example was described in which a film is formed using a substrate processing apparatus having a hot wall type processing furnace.
• the present disclosure is not limited to the above-described embodiments, 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.
• the above embodiments and modifications 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-mentioned aspect and modification.

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• 2022
  • 2022-08-29 JP JP2024543623A patent/JPWO2024047713A1/ja active Pending
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  • 2022-08-29 WO PCT/JP2022/032455 patent/WO2024047713A1/ja not_active Ceased
  • 2022-08-29 CN CN202280096851.3A patent/CN119325640A/zh active Pending
• 2023
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• 2025
  • 2025-02-20 US US19/058,670 patent/US20250232975A1/en active Pending

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