WO2019039127A1 - Procédé de production de semi-conducteur, appareil de traitement de substrat et programme - Google Patents

Procédé de production de semi-conducteur, appareil de traitement de substrat et programme Download PDF

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Publication number
WO2019039127A1
WO2019039127A1 PCT/JP2018/026286 JP2018026286W WO2019039127A1 WO 2019039127 A1 WO2019039127 A1 WO 2019039127A1 JP 2018026286 W JP2018026286 W JP 2018026286W WO 2019039127 A1 WO2019039127 A1 WO 2019039127A1
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WIPO (PCT)
Prior art keywords
layer
gas
substrate
recess
termination
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PCT/JP2018/026286
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English (en)
Japanese (ja)
Inventor
勝吉 原田
島本　聡
良知 橋本
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株式会社日立国際電気
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Priority to JP2019537981A priority Critical patent/JP6752976B2/ja
Publication of WO2019039127A1 publication Critical patent/WO2019039127A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
    • 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
    • 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
    • C23C16/42—Silicides
    • 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
    • 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
    • C23C16/50—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 using electric discharges
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers

Definitions

  • the present invention relates to a method of manufacturing a semiconductor device, a substrate processing apparatus, and a program.
  • a film forming process may be performed in which a nitride film is formed on a pattern including a recess formed on a surface of a substrate such as a hole or a trench (see, for example, Patent Document 1).
  • a technique is provided in which the N termination rate at the top of the recess of the second layer is higher than the N termination rate at the bottom of the recess of the second layer.
  • a nitride film when a nitride film is formed on a pattern including a recess formed on the surface of a substrate, it is possible to form a nitride film over the recess while holding a desired non-film formation region in the recess. It becomes.
  • FIG. 2 is a schematic block diagram of a vertical processing furnace of a substrate processing apparatus suitably used in an embodiment of the present invention, the processing furnace portion being a sectional view taken along the line AA of FIG.
  • the controller of the substrate processing apparatus suitably used by one Embodiment of this invention, and is a figure which shows the control system of a controller with a block diagram. It is a figure which shows the film-forming sequence of one Embodiment of this invention.
  • (A) is a schematic diagram which shows the surface state of the 2nd layer formed in the trench upper part
  • (b) is a schematic diagram which shows the surface state of the 2nd layer formed in the trench bottom part
  • (d) is a modification of the NH termination in the second layer formed in the bottom of the trench
  • (E) is a schematic diagram which shows a mode that source gas is supplied with respect to the 2nd layer after the modification
  • 2.) is a schematic view showing how source gas is supplied to the second layer formed at the bottom of the trench.
  • FIG. 1 A) to (c) are wafer cross-sectional enlarged views showing a state in the middle of forming a cap film on a substrate having a pattern including a trench formed on the surface, and (d) is a cap film It is a wafer cross section enlarged view which shows a mode that the air gap was formed in the trench by forming. It is a figure which shows the film-forming sequence of other embodiment of this invention.
  • the processing furnace 202 has a heater 207 as a heating mechanism (temperature adjustment unit).
  • the heater 207 has a cylindrical shape, and is vertically installed by being supported by the holding plate.
  • the heater 207 also functions as an activation mechanism (excitation unit) that thermally activates (excites) the gas.
  • a reaction tube 203 is disposed concentrically with the heater 207.
  • the reaction tube 203 is made of, for example, a heat resistant material such as quartz (SiO 2 ) or silicon carbide (SiC), and is formed in a cylindrical shape whose upper end is closed and whose lower end is open.
  • a manifold 209 is disposed concentrically with the reaction tube 203.
  • the manifold 209 is made of, for example, a metal material such as stainless steel (SUS), and is formed in a cylindrical shape whose upper and lower ends are open. The upper end portion of the manifold 209 is engaged with the lower end portion of the reaction tube 203, and is configured to support the reaction tube 203.
  • An O-ring 220 a as a seal member is provided between the manifold 209 and the reaction tube 203.
  • the reaction tube 203 is vertically installed similarly to the heater 207.
  • a processing vessel (reaction vessel) is mainly constituted by the reaction tube 203 and the manifold 209.
  • a processing chamber 201 is formed in a cylindrical hollow portion of the processing container. The processing chamber 201 is configured to be able to accommodate a wafer 200 as a substrate.
  • nozzles 249a and 249b are provided to penetrate the side wall of the manifold 209.
  • Gas supply pipes 232a and 232b are connected to the nozzles 249a and 249b, respectively.
  • mass flow controllers (MFC) 241a and 241b which are flow controllers (flow control units) and valves 243a and 243b which are on-off valves are provided in this order from the upstream side of the gas flow.
  • Gas supply pipes 232c and 232d are connected to the gas supply pipes 232a and 232b, respectively, downstream of the valves 243a and 243b.
  • MFCs 241c and 241d and valves 243c and 243d are provided in this order from the upstream side of the gas flow.
  • the nozzles 249 a and 249 b are provided in an annular space in plan view between the inner wall of the reaction tube 203 and the wafer 200, along the upper portion from the lower portion of the inner wall of the reaction tube 203. It is provided to rise upward in the loading direction. That is, the nozzles 249a and 249b are provided along the wafer array area in the area horizontally surrounding the wafer array area on the side of the wafer array area in which the wafers 200 are arrayed.
  • Gas supply holes 250a and 250b for supplying gas are respectively provided on side surfaces of the nozzles 249a and 249b.
  • the gas supply holes 250 a are opened toward the center of the reaction tube 203, and can supply gas toward the wafer 200.
  • the gas supply holes 250 b are opened to face the center of a buffer chamber 237 described later.
  • a plurality of gas supply holes 250 a and 250 b are provided from the lower portion to the upper portion of the reaction tube 203.
  • the nozzle 249 b is provided in a buffer chamber 237 which is a gas dispersion space.
  • the buffer chamber 237 is formed between the inner wall of the reaction tube 203 and the partition wall 237a.
  • the buffer chamber 237 (partition wall 237 a) is in the annular space in plan view between the inner wall of the reaction tube 203 and the wafer 200, and in the portion extending from the lower portion to the upper portion of the inner wall of the reaction tube 203.
  • the buffer chamber 237 (partition wall 237a) is provided on the side of the wafer arrangement area, in the area horizontally surrounding the wafer arrangement area, along the wafer arrangement area.
  • a gas supply hole 250c for supplying a gas is provided at an end of the surface of the partition wall 237a facing (adjacent to) the wafer 200.
  • the gas supply holes 250 c are opened toward the center of the reaction tube 203, and can supply gas toward the wafer 200.
  • a plurality of gas supply holes 250 c are provided from the lower portion to the upper portion of the reaction tube 203.
  • a raw material gas that is, silicon (Si) as a main element constituting a film to be formed as a raw material gas containing an amino group, and an aminosilane-based gas containing an amino group are included in the MFC 241a and valve 243a.
  • the raw material gas is a gaseous raw material, for example, a gas obtained by vaporizing a raw material in a liquid state at normal temperature and pressure, and a raw material in a gaseous state at normal temperature and pressure.
  • the aminosilane-based gas also includes aminosilane containing chlorine (Cl) (silane having both a chloro group and an amino group), but as the aminosilane-based gas in the present embodiment, a Cl-free (Cl-free) aminosilane-based gas Can be used. More preferably, a halogen-free (halogen-free) aminosilane-based gas can be used.
  • the aminosilane-based gas acts as a Si source.
  • As the aminosilane-based gas for example, tris (dimethylamino) silane (SiH [N (CH 3 ) 2 ] 3 , abbreviation: 3DMAS) gas can be used.
  • a nitrogen (N) -containing gas is supplied as a reaction gas into the processing chamber 201 via the MFC 241 b, the valve 243 b, the nozzle 249 b, and the buffer chamber 237.
  • N nitrogen
  • a hydrogen nitride based gas can be used as the N-containing gas.
  • the hydrogen nitride-based gas is also a substance composed of only two elements of N and hydrogen (H), and acts as a nitriding gas, that is, an N source.
  • ammonia (NH 3 ) gas can be used as the hydrogen nitride-based gas.
  • Nitrogen (N 2 ) gas is introduced from the gas supply pipes 232 c and 232 d into the processing chamber 201 through the MFCs 241 c and 241 d, the valves 243 c and 243 d, the gas supply pipes 232 a and 232 b, the nozzles 249 a and 249 b, and the buffer chamber 237, respectively. Supplied.
  • the N 2 gas acts as a purge gas or a carrier gas.
  • the N 2 gas supplied from the gas supply pipe 232 d also acts as a reformed gas by being plasma-excited in step C described later.
  • a source gas supply system is mainly configured by the gas supply pipe 232a, the MFC 241a, and the valve 243a.
  • a hydrogen nitride-based gas supply system is mainly configured by the gas supply pipe 232b, the MFC 241b, and the valve 243b.
  • a nitrogen gas supply system is mainly configured by the gas supply pipes 232c and 232d, the MFCs 241c and 241d, and the valves 243c and 243d.
  • any or all of the supply systems may be configured as an integrated supply system 248 in which the valves 243a to 243d, the MFCs 241a to 241d, and the like are integrated.
  • the integrated supply system 248 is connected to each of the gas supply pipes 232a to 232d, and supplies various gases into the gas supply pipes 232a to 232d, that is, opens and closes the valves 243a to 243d or the MFCs 241a to 241d.
  • the flow rate adjustment operation and the like are configured to be controlled by a controller 121 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 232 a to 232 d etc. in units of integrated units. Maintenance, replacement, addition, and the like can be performed in units of integrated units.
  • two rod-like electrodes 269 and 270 having elongated structures are made up from the lower to the upper side in the loading direction of the wafer 200 from the lower part of the inner wall of the reaction tube 203. As it is provided respectively.
  • the rod-like electrodes 269 and 270 are provided in parallel with the nozzle 249 b.
  • the rod-like electrodes 269 and 270 are each protected by being covered by the electrode protection tube 275 from the upper part to the lower part.
  • One of the rod-like electrodes 269 and 270 is connected to the high frequency power supply 273 via the matching unit 272, and the other is connected to the ground which is a reference potential.
  • the rod-like electrodes 269 and 270 and the electrode protection tube 275 mainly constitute a plasma excitation unit (activation mechanism) that excites (activates) a gas to a plasma state.
  • the matching unit 272 and the high frequency power supply 273 may be included in the plasma excitation unit.
  • An exhaust pipe 231 for exhausting the atmosphere in the processing chamber 201 is connected to the lower side wall of the reaction pipe 203.
  • the exhaust pipe 231 is provided with a pressure sensor 245 as a pressure detector (pressure detection unit) for detecting the pressure in the processing chamber 201 and an APC (Auto Pressure Controller) valve 244 as a pressure regulator (pressure adjustment unit).
  • the vacuum pump 246 as an evacuation apparatus is connected.
  • the APC valve 244 can perform vacuum evacuation and vacuum evacuation stop inside the processing chamber 201 by opening and closing the valve while operating the vacuum pump 246, and further, with the vacuum pump 246 operating,
  • the pressure in the processing chamber 201 can be adjusted by adjusting the valve opening based on the pressure information detected by the pressure sensor 245.
  • An exhaust system is mainly configured by the exhaust pipe 231, the APC valve 244, and the pressure sensor 245.
  • the vacuum pump 246 may be included in the exhaust system.
  • a seal cap 219 is provided as a furnace port that can close the lower end opening of the manifold 209 in an airtight manner.
  • the seal cap 219 is made of, for example, a metal material such as SUS, and is formed in a disk shape.
  • an O-ring 220b is provided as a seal member that contacts the lower end of the manifold 209.
  • a rotation mechanism 267 for rotating a boat 217 described later is installed below the seal cap 219.
  • 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 wafer 200 by rotating the boat 217.
  • the seal cap 219 is configured to be vertically lifted and lowered by a boat elevator 115 as a lift mechanism installed outside the reaction tube 203.
  • the boat elevator 115 is configured as a transfer device (transfer mechanism) that carries the wafer 200 into and out of the processing chamber 201 by moving the seal cap 219 up and down.
  • a shutter 219s as a furnace cover capable of airtightly closing the lower end opening of the manifold 209 in a state where the seal cap 219 is lowered and the boat 217 is carried out from inside the processing chamber 201.
  • the shutter 219s is made of, for example, a metal material such as SUS, and is formed in a disk shape.
  • An O-ring 220c is provided on the top surface of the shutter 219s as a seal member that abuts on the lower end of the manifold 209.
  • the opening / closing operation of the shutter 219s (lifting operation, rotation operation, etc.) is controlled by the shutter opening / closing mechanism 115s.
  • the boat 217 as a substrate support supports a plurality of, for example, 25 to 200 wafers 200 in a horizontal posture and vertically aligned with multiple centers aligned with one another, ie, It is configured to arrange at intervals.
  • the boat 217 is made of, for example, a heat resistant material such as quartz or SiC.
  • a heat insulating plate 218 made of a heat resistant material such as quartz or SiC is supported in multiple stages.
  • a temperature sensor 263 as a temperature detector is installed in the reaction tube 203.
  • the temperature sensor 263 is provided along the inner wall of the reaction tube 203.
  • the controller 121 which is a control unit (control means), is configured as a computer including a central processing unit (CPU) 121a, a random access memory (RAM) 121b, a storage device 121c, and an I / O port 121d. It is done.
  • 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 the internal bus 121e.
  • An input / output device 122 configured as, for example, a touch panel or the like is connected to the controller 121.
  • the storage device 121 c is configured by, for example, a flash memory, a hard disk drive (HDD), or the like.
  • a control program for controlling the operation of the substrate processing apparatus, and a process recipe in which a procedure, conditions, and the like of a film forming process described later are described are readably stored.
  • the process recipe is a combination of processes that causes the controller 121 to execute each procedure in the film formation process described later so as to obtain a predetermined result, and functions as a program.
  • the process recipe, the control program and the like are collectively referred to simply as a program.
  • the process recipe is simply referred to as a recipe.
  • the RAM 121 b is configured as a memory area (work area) in which programs and data read by the CPU 121 a are temporarily stored.
  • the I / O port 121d includes the above-described MFCs 241a to 241d, valves 243a to 243d, pressure sensors 245, APC valves 244, vacuum pumps 246, temperature sensors 263, heaters 207, rotation mechanisms 267, boat elevators 115, shutter opening and closing mechanisms 115s, It is connected to the matching unit 272, the high frequency power source 273, and the like.
  • the CPU 121a is configured to read out and execute the control program from the storage device 121c, and to read out the recipe from the storage device 121c in response to the input of the operation command from the input / output device 122 or the like.
  • the CPU 121a adjusts the flow rates of various gases by the MFCs 241a to 241d, opens and closes the valves 243a to 243d, opens and closes the APC valve 244, and adjusts the pressure by the APC valve 244 based on the pressure sensor 245 in accordance with the contents of the read recipe.
  • the controller 121 installs the above program stored in an external storage device (for example, a magnetic disk such as HDD, an optical disk such as CD, an optical magnetic disk such as MO, a semiconductor memory such as USB memory) 123 in a computer Can be configured by
  • the storage device 121 c 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 when the term "recording medium" is used in the present specification, when only the storage device 121c is included, only the external storage device 123 may be included, or both of them may be included.
  • 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.
  • FIG. explain.
  • a substrate having a pattern including a trench as an example of a recess formed on the surface thereof as the wafer 200
  • the operation of each part constituting the substrate processing apparatus is controlled by the controller 121.
  • step C the N termination rate at the top of the trench in the second layer is made higher than the N termination rate at the bottom of the trench in the second layer.
  • the thickness of the layer formed in the upper portion of the trench (the layer formed by laminating the modified second layer) is set to the layer formed in the bottom of the trench (modified second layer). It is possible to form a SiN film as a nitride film while making it thicker than the thickness of the layer in which the layers are stacked.
  • an insulating film having predetermined characteristics with low capacitance is required.
  • a film such as a gate spacer
  • k value electrical insulation and low relative dielectric constant
  • a silicon nitride film (k value: 7.5 to) or the like is used as an insulating film
  • a silicon oxide film (k value: 3.9) is known as one having a further lower dielectric constant.
  • a film having both a lower dielectric constant (k value of less than 3.9) and an insulating property since the relative dielectric constant of air is 1, by making an interlayer the layer whose insulation is desired to be an air gap, it is possible to achieve both low electrostatic capacity and insulation.
  • a method of forming an air gap between layers a method of selectively removing a film after film formation processing may be considered, but not only an apparatus for film formation processing but also an apparatus for etching processing is necessary. As a result, there are issues such as a decrease in production efficiency and an increase in production cost.
  • the air gap can be formed in the trench without performing the etching process or the like, whereby the insulating film with low capacitance can be formed with high productivity and low production cost. It becomes possible.
  • wafer When the term “wafer” is used in the present specification, it may mean the wafer itself or a laminate of the wafer and a predetermined layer or film formed on the surface thereof.
  • surface of wafer When the term “surface of wafer” is used in the present specification, it may mean the surface of the wafer itself or the surface of a predetermined layer or the like formed on the wafer.
  • the phrase “forming a predetermined layer on the wafer” means that the predetermined layer is directly formed on the surface of the wafer itself, or a layer formed on the wafer, etc. It may mean forming a predetermined layer on top of.
  • substrate in this specification is also synonymous with the use of the word "wafer”.
  • the vacuum pump 246 evacuates (depressurizes and evacuates) the processing chamber 201, that is, the space in which the wafer 200 exists has a desired pressure (vacuum degree).
  • the pressure in the processing chamber 201 is measured by the pressure sensor 245, and the APC valve 244 is feedback-controlled based on the measured pressure information.
  • the wafer 200 in the processing chamber 201 is heated by the heater 207 so as to have a desired processing temperature.
  • the degree of 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.
  • the rotation of the wafer 200 by the rotation mechanism 267 is started.
  • the operation of the vacuum pump 246 and the heating and rotation of the wafer 200 are both continued at least until the processing of the wafer 200 is completed.
  • steps AC (Deposition step) Thereafter, the next three steps, ie, steps AC, are sequentially performed.
  • Step A In this step, 3DMAS gas is supplied to the wafer 200 in the processing chamber 201.
  • valve 243a is opened to flow the 3DMAS gas into the gas supply pipe 232a.
  • the flow rate of the 3DMAS gas is adjusted by the MFC 241 a, supplied into the processing chamber 201 via the nozzle 249 a, and exhausted from the exhaust pipe 231.
  • 3DMAS gas is supplied to the wafer 200.
  • the valves 243c and 243d may be opened to flow the N 2 gas into the gas supply pipes 232c and 232d.
  • the flow rate of the N 2 gas is adjusted by the MFCs 241 c and 241 d, and is supplied into the processing chamber 201 via the nozzles 249 a and 249 b and the buffer chamber 237.
  • 3 DMAS gas supply flow rate 10 to 1000 sccm N 2 gas supply flow rate (for each gas supply pipe): 0 to 10000 sccm
  • Each gas supply time 1 to 100 seconds
  • a Si-containing layer containing an amino group is formed on the outermost surface of the wafer 200 as a first layer.
  • the Si-containing layer containing an amino group is formed by the physical adsorption of 3DMAS, the chemical decomposition of a substance in which a part of 3DMAS is decomposed, the thermal decomposition of 3DMAS, etc. on the outermost surface of the wafer 200 .
  • the Si-containing layer containing an amino group is formed by, for example, chemisorption of Si on the outermost surface of the wafer 200 in 3DMAS in a state where a part of the ligand is eliminated.
  • the Si-containing layer containing an amino group is also simply referred to as a Si-containing layer.
  • the valve 243 a is closed to stop the supply of 3DMAS gas into the processing chamber 201. Then, the inside of the processing chamber 201 is evacuated to exhaust the gas and the like remaining in the processing chamber 201 from the inside of the processing chamber 201. At this time, the valves 243 c and 243 d are opened to supply N 2 gas into the processing chamber 201.
  • the N 2 gas acts as a purge gas.
  • purge gas in addition to N 2 gas, for example, various rare gases such as Ar gas, He gas, Ne gas, and Xe gas can be used. This point is the same in Steps B and C described later.
  • Step B plasma-excited NH 3 gas (NH 3 * ) is supplied to the wafer 200 in the processing chamber 201, that is, the first layer formed on the wafer 200.
  • the opening and closing control of the valves 243b, 243c, and 243d is performed in the same procedure as the opening and closing control of the valves 243a, 243c, and 243d in step A.
  • the flow rate of the NH 3 gas is adjusted by the MFC 241 b, supplied into the processing chamber 201 through the nozzle 249 b and the buffer chamber 237, and exhausted from the exhaust pipe 231.
  • NH 3 gas (NH 3 * ) plasma-excited is supplied to the wafer 200.
  • the NH 3 gas is excited (activated) by plasma when passing through the buffer chamber 237, and at this time, an active species such as NH 3 * is generated, and this active species is supplied to the wafer 200. It will be.
  • plasma-excited NH 3 gas is also referred to as NH 3 * for convenience.
  • NH 3 gas supply flow rate 100 to 10000 sccm
  • NH 3 gas supply time 1 to 100 seconds
  • Processing pressure 1 to 2000 Pa
  • RF power 50 to 1000W Is illustrated.
  • Other processing conditions are the same as the processing conditions in step A.
  • the processing conditions exemplified here are conditions under which active NH 3 * can be evenly distributed not only to the top of the trench formed on the surface of the wafer 200 but also to the bottom of the trench and the periphery thereof.
  • FIG. 5 (a) is a schematic view showing the surface condition of the second layer formed at the top of the trench
  • FIG. 5 (b) is a schematic diagram showing the surface condition of the second layer formed at the bottom of the trench is there.
  • active NH 3 * can be supplied to the entire surface of the first layer in the active state without being inactivated.
  • the surface of the second layer obtained by nitriding the first layer can be uniformly NH-terminated from the top to the bottom of the trench. That is, in this step, the NH 3 * concentration at the top of the trench is made equal to the NH 3 * concentration at the bottom of the trench. Further, in this step, even if the active NH 3 * is inactivated, NH 3 * ratio of deactivation of the trench bottom is set to be equal to the NH 3 * deactivation rate in the upper portion of the trench. Note that when forming the second layer, impurities such as C and H contained in the first layer are extracted or eliminated from the first layer in the process of the nitridation reaction with NH 3 *. Separate from the first layer.
  • the valve 243 b is closed, and the application of the RF power between the rod-like electrodes 269 and 270 is stopped, and the NH 3 into the processing chamber 201 is Stop the supply of * . Then, the gas and the like remaining in the processing chamber 201 are removed from the inside of the processing chamber 201 by the same processing procedure as in step A.
  • hydrogen nitride gas such as diazene (N 2 H 2 ) gas, hydrazine (N 2 H 4 ) gas, N 3 H 8 gas and the like can be used besides NH 3 gas.
  • Step C After step B is completed, plasma-excited N 2 gas (N 2 * ) is supplied to the wafer 200 in the processing chamber 201, that is, the second layer whose surface is NH-terminated.
  • the valve 243d is opened to flow N 2 gas into the gas supply pipe 232d.
  • the flow rate of the N 2 gas is adjusted by the MFC 241 d, and is supplied into the processing chamber 201 through the nozzle 249 b and the buffer chamber 237 and exhausted through the exhaust pipe 231.
  • plasma-excited N 2 gas (N 2 * ) is supplied to the wafer 200.
  • the N 2 gas is excited (activated) by plasma when passing through the buffer chamber 237, at which time an active species such as N 2 * is generated, and this active species is supplied to the wafer 200. It will be.
  • plasma-excited N 2 gas is also referred to as N 2 * for convenience.
  • Plasma excitation N 2 gas supply flow rate 10 to 5000 sccm
  • Plasma excitation N 2 gas supply time 1 to 90 seconds
  • Processing pressure 10 to 2666 Pa
  • RF power 1 to 500 W Is illustrated.
  • Other processing conditions are the same as the processing conditions in step A.
  • the processing conditions exemplified here are conditions under which active N 2 * can be mainly supplied only to the upper portion of the trench and the periphery thereof. That is, the conditions are such that it is possible to deactivate N 2 * before reaching the trench bottom and its periphery, and to supply little or no active N 2 * to these regions. .
  • the processing conditions exemplified here are such that the N 2 * concentration at the top of the trench is higher than the N 2 * concentration at the bottom of the trench, and the N 2 * deactivation rate at the bottom of the trench is the top of the trench It is also a condition that becomes larger than the N 2 * inactivation rate in
  • N 2 * By supplying N 2 * to the wafer 200 under the conditions described above, it becomes possible to modify part of the surface of the second layer formed on the wafer 200 in step B. That is, among NH terminations present on the surface of the second layer, it is possible to desorb H from part of the NH terminations and reform (change) this to N terminations.
  • the active N 2 * is mainly supplied only to the upper portion of the trench and its periphery, and is hardly or completely supplied to the trench lower portion and its periphery.
  • FIG. 5C is a schematic view showing how a part of the NH termination in the second layer formed in the upper part of the trench is reformed into an N termination
  • FIG. 5D is formed in the bottom of the trench. It is a schematic diagram which shows a mode that it maintains with NH termination
  • this step it is possible to make the N termination rate at the top of the trench in the second layer higher than the N termination rate at the bottom of the trench in the second layer. Also, by performing this step, it is possible to make the NH termination rate at the bottom of the trench in the second layer higher than the NH termination rate at the top of the trench in the second layer. That is, by performing this step, it is possible to make the N / NH termination ratio at the top of the trench in the second layer larger than the N / NH termination ratio at the bottom of the trench in the second layer.
  • the N termination rate referred to here is the N termination amount (the number of N terminations present on the surface) and the NH termination amount (the number of NH terminations present on the surface) per unit area of the surface of the second layer.
  • the N-terminus present on the surface of the second layer acts to promote the adsorption of Si contained in the 3DMAS gas to the surface of the second layer when performing step A in the next cycle.
  • the NH termination present on the surface of the second layer acts to suppress the adsorption of Si contained in 3DMAS gas on the surface of the second layer when performing step A in the next cycle. .
  • the N termination rate at the top of the second layer trench is higher than the N termination rate at the bottom of the second layer trench, that is, the NH termination rate at the bottom of the second layer trench is
  • 5 (e) is a schematic view showing how 3DMAS gas is supplied to the second layer (the second layer whose surface is reformed to the N terminal) formed in the upper part of the trench.
  • f) is a schematic diagram which shows a mode that 3 DMAS gas is supplied with respect to the 2nd layer (2nd layer in which the surface was maintained with NH termination
  • Si contained in the 3DMAS gas is the second layer It adsorbs to the N terminal which exists in the surface of.
  • the surface of the second layer is NH-terminated, even if part of the Si-N bond contained in the 3DMAS gas is broken and part of the ligand is desorbed, the NH-terminus of the surface of the second layer If the N—H bond is not broken, Si contained in the 3DMAS gas will not be adsorbed on the surface of the second layer.
  • the thicknesses of the first layer and the second layer formed on the top of the trench in the next cycle are respectively thicker than the thicknesses of the first layer and the second layer formed on the bottom of the trench in the next cycle. That is, the thickness of the SiN layer formed at the top of the trench per cycle is larger than the thickness of the SiN layer formed at the bottom of the trench per cycle.
  • the N termination rate in the upper portion of the trench in the second layer is made higher than the NH termination rate in the upper portion of the trench in the second layer by optimizing the processing conditions for supplying N 2 *. Is possible. Also, the NH termination rate at the trench bottom of the second layer can be made higher than the N termination rate at the trench bottom of the second layer.
  • the above-described effect of suppressing the formation of the first layer on the bottom of the trench while obtaining the formation of the first layer on the top of the trench is more reliably obtained. Be able to That is, the cap film can be more reliably grown on the upper portion of the trench, the desired non-film formation region can be reliably held in the trench, and an appropriate air gap can be formed.
  • step C active N 2 * is mainly supplied only to the upper part of the trench and its periphery, and is hardly supplied at all (does not reach) to the trench lower part and its periphery. It is important to do step C. For example, if the process pressure in step C is made larger than the process pressure in step B, it is possible to appropriately shorten the lifetime of active N 2 * , and the effect described here is surely obtained. Be able to Also, for example, even if the RF power in step C is made smaller than the RF power in step B, it is possible to appropriately shorten the lifetime of active N 2 * , and the effect described here is surely It will be obtained.
  • step C if the supply time of N 2 * in step C is made shorter than the supply time of NH 3 * in step B, the arrival probability of the active N 2 * to the bottom of the trench and its periphery is reduced. To ensure that the effects described here can be obtained.
  • the valve 243 d is closed, and the application of the RF power between the rod-shaped electrodes 269 and 270 is stopped, and the processing is performed into the processing chamber 201. Stop the supply of N 2 * . Then, the gas and the like remaining in the processing chamber 201 are removed from the inside of the processing chamber 201 by the same processing procedure as in step A.
  • [Performed number of times] 6A to 6D by performing a predetermined number of times (n times, n is an integer greater than or equal to 1) a cycle in which steps A to C described above are performed not simultaneously, that is, alternately without synchronization.
  • the SiN film 300 is formed on the pattern including the trench formed on the surface of the wafer 200, and at this time, without filling the trench with the SiN film 300, the cap film of the SiN film 300 is formed on the trench It becomes possible to form.
  • an air gap 400 is formed in the trench.
  • N 2 gas as a purge gas is supplied from the gas supply pipes 232 c and 232 d into the processing chamber 201 and exhausted from the exhaust pipe 231.
  • the inside of the processing chamber 201 is purged, and gas and reaction byproducts remaining in the processing chamber 201 are removed from the inside of the processing chamber 201 (after purge).
  • the atmosphere in the processing chamber 201 is replaced with the inert gas (inert gas substitution), and the pressure in the processing chamber 201 is returned to normal pressure (atmospheric pressure recovery).
  • the seal cap 219 is lowered by the boat elevator 115, and the lower end of the manifold 209 is opened. Then, the processed wafer 200 is carried out (boat unloading) from the lower end of the manifold 209 to the outside of the reaction tube 203 while being supported by the boat 217. 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). The processed wafer 200 is carried out of the reaction tube 203 and then taken out of the boat 217 (wafer discharge).
  • step C After forming the second layer whose surface is NH-terminated, performing the step C makes the N termination rate at the top of the trench in the second layer higher than the N termination rate at the bottom of the trench in the second layer It becomes possible.
  • the growth of the SiN layer in the upper part of the trench can be promoted, and the SiN film can be formed as the cap film in the upper part of the trench without filling the inside of the trench with the SiN film.
  • Step C After forming the second layer whose surface is NH-terminated, performing Step C makes the NH termination rate at the bottom of the trench in the second layer higher than the NH termination rate at the top of the trench in the second layer It becomes possible. As a result, the growth of the SiN layer at the bottom of the trench can be suppressed, and when forming a SiN film as a cap film on the upper part of the trench, it becomes possible to hold a desired non-film formation region in the trench. It is possible to make it possible not to embed the SiN film. As a result, it is possible to form an air gap in the trench.
  • Step C After forming the second layer whose surface is NH-terminated, performing Step C causes the N / NH termination ratio at the top of the trench in the second layer to be the N / NH termination ratio at the bottom of the trench in the second layer. It is possible to make it larger. This makes it possible to reliably advance the growth of the cap film on the upper portion of the trench and to form an air gap in the trench without filling the inside of the trench with the SiN film.
  • the NH 3 gas may be thermally excited and supplied instead of being plasma-excited and supplied.
  • Modification 2 Further, for example, as in the film formation sequence shown in FIG. 7 and the following, the order of flowing the gas may be changed.
  • Modification 3 Further, for example, as in the film formation sequence shown below, the order of gas flow may be changed.
  • the same effect as the film forming sequence shown in FIG. 4 can be obtained. That is, it is possible to form a SiN film as a cap film on the upper part of the trench while suppressing the burying in the trench by the SiN film, and to form an air gap in the trench. Also in these modifications, the processing pressure in step C is made larger than the processing pressure in step B, the RF power in step C is made smaller than the RF power in step B, and the N 2 * supply time in step C the by shorter than the NH 3 gas supply time in the step B, so that this effect can be obtained more reliably.
  • the adsorption of Si to the upper portion of the trench and its periphery can be promoted from the first cycle, and the adsorption of Si to the trench bottom and its periphery can be suppressed from the first cycle. Therefore, this effect can be obtained more efficiently.
  • the processing pressure in step C may be gradually reduced as the cycle is repeated while the pressure being higher than the processing pressure in step B.
  • the RF power in step C may be gradually increased as the cycle is repeated while the power smaller than the RF power in step B is used.
  • the N 2 * supply time in step C may be made shorter as the NH 3 * supply time in step B shorter than the NH 3 * supply time in step B.
  • step C may be performed only in the initial to middle stages, and step C may not be performed in the middle to late stages.
  • the present invention is suitably applied not only in the case of forming a metalloid nitride film containing a metalloid element such as silicon as a main element but also in the case of forming a metal nitride film containing a metal element as a main element.
  • the present invention uses an aluminum nitride film (AlN) as an insulating film using a raw material such as tris (diethylamino) aluminum (Al [N (C 2 H 5 ) 2 ] 3 , abbreviation: TDEAA, etc. as shown below.
  • TDEAA tris (diethylamino) aluminum
  • membrane it can apply suitably.
  • the processing procedure and processing conditions of the film forming process at this time can be the same as the processing procedure and processing conditions of the above-described embodiment and modification. Also in these cases, the same effect as the above-described embodiment and modification can be obtained.
  • the present invention can be suitably applied to the case where a wafer having a pattern including concave portions such as holes in addition to concave portions such as trenches is used as the wafer 200.
  • the “trench” in the above description may be replaced with the “hole”. Also in this case, the same effect as the above-described embodiment and modification can be obtained.
  • the recipe used for substrate processing be individually prepared according to the processing content, and stored in the storage device 121 c via the telecommunication line or the external storage device 123. Then, when the substrate processing is started, it is preferable that the CPU 121a appropriately select an appropriate recipe from among the plurality of recipes stored in the storage device 121c in accordance with the content of the substrate processing.
  • the burden on the operator can be reduced, and processing can be quickly started while avoiding an operation error.
  • the above-described recipe is not limited to the case of creating a new one, and may be prepared, for example, by changing an existing recipe already installed in the substrate processing apparatus.
  • the changed recipe may be installed in the substrate processing apparatus via the telecommunication line or the recording medium recording the recipe.
  • the existing recipe that has already been installed in the substrate processing apparatus may be directly changed by operating the input / output device 122 provided in the existing substrate processing apparatus.
  • the example which forms a film using the batch type substrate processing apparatus which processes a plurality of substrates at once was explained.
  • the present invention is not limited to the above-described embodiment, and can be suitably applied to, for example, the case where a film is formed using a sheet-fed substrate processing apparatus that processes one or several substrates at a time.
  • the example of forming the film using the substrate processing apparatus having the hot wall type processing furnace has been described.
  • the present invention is not limited to the above-described embodiment, and can be suitably applied to the case of forming a film using a substrate processing apparatus having a cold wall type processing furnace.
  • film formation can be performed under the same processing procedure and processing conditions as those of the above-described embodiment and modification, and the same effects as these can be obtained.
  • processing procedure and processing conditions at this time can be, for example, the same as the processing procedure and processing conditions of the above-described embodiment.

Abstract

Selon la présente invention, lors de la formation d'un film de nitrure sur un motif qui comprend une indentation formée dans la surface d'un substrat, le film de nitrure est formé sur l'indentation tandis qu'une région de non-formation de film souhaitée est maintenue à l'intérieur de l'indentation. La présente invention concerne un procédé de formation d'un film de nitrure sur un substrat par répétition non simultanée d'un cycle comprenant (a) une étape consistant à former une première couche par application d'un gaz de charge d'alimentation contenant un groupe amino au substrat comportant une indentation formée dans sa surface, (b) une étape consistant à exécuter une nitruration de la première couche par application d'un gaz à base de nitrure d'hydrogène au substrat de manière à former une seconde couche à terminaison NH, et (c) une étape consistant à reformer une partie de la terminaison NH dans la seconde couche en une terminaison N par application d'un gaz d'azote excité par plasma au substrat tandis qu'une autre partie de la terminaison NH, qui est différente de la partie susmentionnée de la terminaison NH, est maintenue telle quelle sans être reformée en une terminaison N, à l'étape (c), la seconde couche étant conçue pour avoir un rapport de terminaison N plus élevé au niveau de la partie supérieure de l'indentation qu'au niveau de la partie inférieure de l'indentation.
PCT/JP2018/026286 2017-08-22 2018-07-12 Procédé de production de semi-conducteur, appareil de traitement de substrat et programme WO2019039127A1 (fr)

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WO2022059505A1 (fr) * 2020-09-16 2022-03-24 東京エレクトロン株式会社 Procédé d'incorporation de film de sin et dispositif de formation de film

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JP2006135069A (ja) * 2004-11-05 2006-05-25 Elpida Memory Inc 半導体装置およびその製造方法
JP2013135154A (ja) * 2011-12-27 2013-07-08 Tokyo Electron Ltd 成膜方法
JP2014075493A (ja) * 2012-10-04 2014-04-24 Tokyo Electron Ltd 成膜方法及び成膜装置
JP2017139451A (ja) * 2016-02-01 2017-08-10 東京エレクトロン株式会社 窒化膜の形成方法
JP2017168786A (ja) * 2016-03-18 2017-09-21 株式会社日立国際電気 半導体装置の製造方法、基板処理装置およびプログラム

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JP2006135069A (ja) * 2004-11-05 2006-05-25 Elpida Memory Inc 半導体装置およびその製造方法
JP2013135154A (ja) * 2011-12-27 2013-07-08 Tokyo Electron Ltd 成膜方法
JP2014075493A (ja) * 2012-10-04 2014-04-24 Tokyo Electron Ltd 成膜方法及び成膜装置
JP2017139451A (ja) * 2016-02-01 2017-08-10 東京エレクトロン株式会社 窒化膜の形成方法
JP2017168786A (ja) * 2016-03-18 2017-09-21 株式会社日立国際電気 半導体装置の製造方法、基板処理装置およびプログラム

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022059505A1 (fr) * 2020-09-16 2022-03-24 東京エレクトロン株式会社 Procédé d'incorporation de film de sin et dispositif de formation de film

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