WO2010103751A1 - 原子層堆積装置及び薄膜形成方法 - Google Patents
原子層堆積装置及び薄膜形成方法 Download PDFInfo
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- WO2010103751A1 WO2010103751A1 PCT/JP2010/001462 JP2010001462W WO2010103751A1 WO 2010103751 A1 WO2010103751 A1 WO 2010103751A1 JP 2010001462 W JP2010001462 W JP 2010001462W WO 2010103751 A1 WO2010103751 A1 WO 2010103751A1
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- container
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- thin film
- internal space
- atomic layer
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- 239000010409 thin film Substances 0.000 title claims abstract description 59
- 238000000231 atomic layer deposition Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims description 51
- 239000000758 substrate Substances 0.000 claims abstract description 135
- 230000007246 mechanism Effects 0.000 claims abstract description 41
- 238000003825 pressing Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000007789 gas Substances 0.000 description 70
- 230000008569 process Effects 0.000 description 22
- 239000010408 film Substances 0.000 description 20
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/568—Transferring the substrates through a series of coating stations
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- 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
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- 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
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
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- 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
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
- C23C16/4409—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber characterised by sealing means
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- 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
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- 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]
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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- 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
- C23C16/46—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 heating the substrate
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- 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
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- 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
- C23C16/54—Apparatus specially adapted for continuous coating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32733—Means for moving the material to be treated
- H01J37/32752—Means for moving the material to be treated for moving the material across the discharge
Definitions
- the present invention relates to an atomic layer deposition (hereinafter also referred to as ALD (Atomic Layer Deposition)) apparatus for forming a thin film on a substrate, and a thin film forming method for forming a thin film on a substrate by an atomic layer deposition method.
- ALD atomic layer Deposition
- the ALD method two types of gas mainly composed of elements constituting a film to be formed are alternately supplied onto a film formation target substrate, and a thin film is formed on the substrate in units of atomic layers repeatedly several times.
- This is a thin film forming technique for forming a film having a desired thickness.
- a source gas containing Si and an oxidizing gas containing O are used.
- a nitriding gas is used instead of the oxidizing gas.
- the ALD method has both high step coverage and film thickness controllability compared to the general CVD (Chemical Vapor Deposition) method. Therefore, it is expected to be put to practical use for forming capacitors for memory elements and insulating films called “high-k gates”.
- an insulating film can be formed at a temperature of 300 ° C. or lower. Therefore, it is expected that the ALD method is applied to formation of a gate insulating film of a thin film transistor of a display device using a glass substrate such as a liquid crystal display.
- Patent Document 1 discloses an ALD apparatus for forming a thin film on a substrate, a source gas adsorption chamber that adsorbs at least one type of source gas to the substrate, and a reaction that irradiates the substrate with at least one type of reactive gas.
- An ALD apparatus having a reactive gas irradiation chamber and means for replacing a substrate between the source gas adsorption chamber and the reactive gas irradiation chamber is described.
- This apparatus is realized as an object to provide an apparatus capable of forming a film efficiently without requiring frequent maintenance of a film formation chamber in vacuum film formation by the ALD method.
- Patent Document 1 since the film forming chamber is divided for each necessary process, neither the source gas adsorption chamber nor the reactive gas irradiation chamber is deposited on the wall surface of the room, as in the prior art. It is described that maintenance of a film forming chamber is unnecessary, and radicals having high reactivity can be used effectively. However, such an apparatus becomes large and the cost increases. In particular, when an 8th generation glass plate having a side exceeding 2 m is used as a target substrate on which a thin film is formed, the installation area and the equipment cost are greatly increased.
- the present invention is different from the ALD apparatus described above in order to reduce costs, and has a single film formation chamber, and an atomic layer deposition apparatus capable of forming a thin film with uniform film quality on a substrate, and An object is to provide a method for forming a thin film.
- An atomic layer deposition apparatus of the present invention is an atomic layer deposition apparatus that forms a thin film on a substrate, a container that forms a first internal space, and a substrate loading / unloading port for loading or unloading a substrate;
- a first container provided at a different position with a gas inlet for introducing a gas for forming a thin film on the substrate into the inside, and provided in the first container and separated from the first internal space
- a second container that forms a second internal space and includes a first opening; a first moving mechanism that moves the second container in a predetermined direction; and a substrate that is loaded or unloaded,
- the first moving mechanism is controlled so that the second container is moved to the position of 2. And having a control unit for, a.
- the thin film forming method of the present invention includes a first container that forms a first internal space, and a second internal space that is provided inside the first container and separated from the first internal space.
- the thin film forming step of forming a thin film by moving to a second position opposite to the gas inlet for introducing the gas forming the gas into the second internal space, and the first opening includes the substrate loading / unloading port. And a substrate unloading step for unloading the substrate. And wherein the door.
- a thin film having a uniform film quality can be formed on a substrate.
- FIG. 1 is a schematic block diagram of the 2nd container of the atomic layer deposition apparatus shown in FIG.
- B is a figure explaining the carrying-in and carrying-out method of a board
- FIG. 1 is a schematic block diagram of the board
- FIG. 2 is a schematic block diagram of the 2nd container of the atomic layer deposition apparatus shown in FIG.
- substrate is a figure explaining the carrying-in and carrying-out method of a board
- substrate carrying-in process of the atomic layer deposition apparatus shown in FIG. 1 is a board
- FIG. 1 shows the state at the time of the cleaning process of the atomic layer deposition apparatus shown in FIG.
- FIG. 1 is a cross-sectional view showing a schematic device configuration of an atomic layer deposition apparatus (hereinafter referred to as an ALD apparatus) 10 for forming a thin film on a substrate 12 during a thin film forming process.
- a source gas such as TMA (Tri-Methyl-Aluminium)
- an oxidizing gas such as ozone O 3
- the ALD apparatus 10 mainly includes a first container 20, a second container 60, and a pressing member 80.
- the first container 20 is an outer container that forms a first inner space 22 that maintains a predetermined pressure.
- the second container 60 is an inner container that is provided inside the first container 20 and forms a second inner space 62 that maintains a predetermined pressure.
- the pressing member 80 separates the second internal space 62 from the first internal space 22 by pressing the second container 60.
- the first container 20 is made of a metal material such as SUS.
- a gas inlet for introducing N 2 gas (or inert gas) into the first internal space 22 is provided on the upper wall of the first container 20.
- An exhaust port to which the exhaust pipe 42 is connected is provided on the upper wall of the first container 20.
- the gas in the first internal space 22 is exhausted to the outside of the first container 20 by an exhaust unit 44 such as a turbo molecular pump. Thereby, the inside of the first internal space 22 is maintained at a predetermined pressure in the atmosphere of the introduced N 2 gas.
- an exhaust unit 44 such as a turbo molecular pump.
- the heater 24 is provided adjacent to the second container 60 above the second container 60 provided inside the first container 20.
- the heater 24 heats the source gas supplied to the substrate 12 placed in the second container 60 and the second inner space 62 through the second container 60.
- the wiring and the like of the heater 24 are drawn out through a through hole provided in the upper portion of the first container 20 and connected to a power source (not shown).
- a heater 25 is provided adjacent to the second container 60 below the second container 60 provided in the first container 20.
- the heater 25 heats the source gas supplied to the substrate 12 placed in the second container 60 and the second inner space 62 through the second container 60.
- the wiring and the like of the heater 25 are drawn out of the first container 20 through a through hole (not shown) and connected to a power source (not shown).
- a substrate loading / unloading port 28 for loading and unloading the substrate 12 is provided on the wall surface 26 (the right side surface in FIG. 1) of the first container 20. Further, a shutter 27 connected to the outside of the first container 20 is provided at a portion extending in the horizontal direction from the substrate loading / unloading port 28 toward the outside of the first container 20. Therefore, when the substrate 12 is carried in, the shutter 27 is opened, and the substrate 12 is carried into the first container 20 through the substrate carry-in / out port 28. When unloading the substrate 12, the shutter 27 is opened, and the substrate 12 is unloaded from the first container 20 through the substrate loading / unloading port 28. The state when the substrate 12 is carried in and out is shown in FIG. A description of FIG. 3 will be given later.
- a gas introduction port 29 for introducing a gas for forming a thin film on the substrate is provided on the wall surface 26 where the substrate loading / unloading port 28 is provided.
- a gas introduction pipe 30 that introduces a source gas or an oxidizing gas into the second internal space 62 is connected to the gas introduction port 29.
- two gas introduction pipes 30a and 30b are connected.
- the gas introduction pipe 30 a introduces a source gas (for example, an organic metal gas such as TMA) or a purge gas (for example, nitrogen gas) into the second internal space 62.
- a source gas for example, an organic metal gas such as TMA
- a purge gas for example, nitrogen gas
- the gas introduction pipe 30 b introduces an oxidizing gas (for example, ozone) or a purge gas (for example, nitrogen gas) into the second internal space 62.
- a plurality of gas inlets 29 are provided at equal intervals in the width direction of the substrate 12 (in the direction perpendicular to the plane of FIG. 1).
- the gas inlet 29 is provided in a wider range than the width direction of the substrate 12.
- the gas introduction port 29 is configured to be positioned vertically above a position in the height direction where a substrate support portion 67 described later is provided.
- a through hole through which an exhaust pipe 68 (described later) passes is provided on the other wall surface (the left surface in FIG. 1) of the first container 20.
- a first moving mechanism 36 for moving the heater 25 in the vertical direction is provided on the bottom surface 32 of the first container 20.
- the heater 25 can be moved in the vertical direction.
- the second container 60 can be supported at a predetermined position by controlling the length of the support mechanism 36a extending from the first moving mechanism 36.
- the first moving mechanism 36 includes a caster 37 and can move in the in-plane direction of the bottom surface 32 of the first container 20.
- the bottom surface 32 of the first container 20 is separable from the wall surface and upper wall of the first container 20.
- Two support mechanisms 38a extending downward in the figure are provided on the bottom surface 32 of the first container 20, and a second moving mechanism 38 such as a hydraulic cylinder is provided on the two support mechanisms 38a.
- the support mechanism 38a of the second moving mechanism 38 includes the bottom surface 32 of the first container 20, the first moving mechanism 36, the heater 25 supported by the support mechanism 36a of the first moving mechanism 36, and the heater 25.
- the second container 60 to be supported is moved in the vertical direction.
- An O-ring 33 is provided between the bottom surface 32 and the wall surface of the first container 20, and the second moving mechanism 38 raises the bottom surface 32, so that the first internal space 22 is directed to the outside. Closed configuration.
- the first moving mechanism 36 and the second moving mechanism 38 are connected to the control unit 100.
- the control unit 100 controls the first moving mechanism 36 and the second moving mechanism 38 so that the second container 60 is at a predetermined position. Details of the control of the moving mechanisms 36 and 38 by the control unit 100 will be described later.
- the substrate loading / unloading port 28, the gas introduction port 29, and the through hole through which the exhaust pipe 68 passes can be made separate openings. Thereby, there is no restriction on the structure of the gas inlet 29 for supplying the source gas uniformly, and a thin film with uniform film quality can be formed.
- FIG. 2A is a schematic configuration diagram of the second container 60.
- the second container 60 is provided inside the first container 20.
- the second container 60 is a cylindrical container that forms the second internal space 62. Quartz is preferably used for the second container 60 from the viewpoint of a stable material.
- the substrate 12 is a glass substrate, the material itself is substantially the same, so there is an advantage that there is no fear that different components adhere to the substrate 12.
- the second container 60 is supported by the support mechanism 36a so as to be positioned horizontally inside the first container 20.
- a first opening 64 through which a source gas for forming a thin film is formed on the substrate 12 is provided at one end of the cylindrical shape.
- the gas inlet 29 provided on the wall surface 26 of the first container 20 and the first opening 64 are in a position facing each other.
- a second opening 66 through which the gas in the second internal space 62 flows out of the second internal space 62 is provided at the end opposite to the side having the first opening 64.
- two second openings 66a and 66b are provided.
- the second opening 66a is provided at a position vertically above a position in the height direction where a substrate support 67 described later is provided.
- the gas flowing out of the second internal space 62 through the second opening 66 passes through a through hole provided in the left wall surface of the first container 20 and passes through an exhaust pipe 68 connected to the through hole.
- the air is exhausted by an exhaust unit 69 such as a vacuum pump.
- an exhaust unit 69 such as a vacuum pump.
- the pressure in the second internal space 62 may be the same pressure as the pressure in the first internal space 22 described above, or may be a different pressure.
- FIG. 2B is a diagram for explaining a method for carrying in and carrying out the substrate 12.
- substrate 12 is mounted in the fork part 70 of the board
- the substrate 12 placed on the fork unit 70 opens and closes the shutter 27, and is carried into and out of the second container 60 through the substrate carry-in / out port 28 and the first opening 64.
- the substrate carry-in process and the substrate carry-out process will be described in detail later.
- a substrate support portion 67 for placing the substrate 12 is provided inside the second container 60.
- the substrate support portion 67 is provided at an intermediate position in the height direction of the second internal space 62. Further, the substrate support portion 67 has a flat surface provided in parallel with the cylindrical longitudinal direction of the second container 60. This plane is used as a substrate mounting surface.
- the shape of the substrate support portion 67 on the first opening 64 side is a comb-like shape corresponding to the fork portion 70 at the substrate placement tip of the transport carriage that carries in and out the substrate 12.
- the large substrate 12 is carried into and out of the second internal space 62 having a low cylindrical shape.
- the substrate 12 can be carried in and out without the surface on which the thin film is formed touching the inner surface of the second container 60.
- the source gas passes over the substrate 12 placed on the substrate support portion 67, and a part thereof is adsorbed on the substrate 12. Further, the activated oxidizing gas in the heated state can oxidize the components of the source gas adsorbed on the substrate 12.
- the pressing member 80 presses the second container 60 in the cylindrical longitudinal direction (horizontal direction).
- An O-ring 86a, a spacer 84, and an O-ring 86b are sequentially provided between the pressing member 80 and the second container 60.
- a square bellows 82 is provided between the left wall surface of the first container 20 in FIG. Therefore, the pressing member 80 can move in the horizontal direction.
- an O-ring 90a, a spacer 88, and an O-ring 90b are sequentially provided between the second container 60 and the wall surface 26 (the right-side surface in FIG. 1) of the first container 20.
- deposition preventing plates 31 and 83 are provided on the inner wall of the wall surface 26 near the gas inlet 29 and the inner wall of the exhaust pipe 68 for preventing the thin film from adhering to the substrate other than the substrate on which the thin film is to be formed. .
- the second container 60 is supported by the first moving mechanism 36 including the casters 37. Therefore, the second container 60 can move in the longitudinal direction of the cylindrical shape.
- the pressing member 80 presses the second container 60 in the longitudinal direction of the cylindrical shape
- the second container 60 is pressed against the first container 20 through the O-rings 86a, 86b, 90a, 90b.
- the second internal space 62 is separated from the first internal space 22. That is, the presser member 80 presses the second container 60 in the longitudinal direction of the cylindrical shape of the second container 60, so that the presser member 80 separates the second internal space 62 from the first internal space 22.
- the first internal space 22 and the second internal space 62 are separated from each other so that the pressure in the first internal space 22 and the pressure in the second internal space 62 can be individually controlled. It means that it is separated.
- the shorter the circumference of the O-ring the more reliably the two spaces can be separated.
- the second container 60 is configured to be pressed in the longitudinal direction of the cylindrical shape of the second container 60, the second internal space 62 is separated from the first internal space 22.
- the required circumference of the O-ring can be shortened according to the cylindrical shape.
- the second container 60 is configured to be pressed in the longitudinal direction of the cylindrical shape of the second container 60, whereby the second inner space 62 of the second container 60 is made to be in relation to the first inner space 22. Can be separated more reliably. Therefore, the source gas can be prevented from leaking from the second internal space 62 to the first internal space 22.
- the pressing member 80 presses the second container 60 in the longitudinal direction of the cylindrical shape of the second container 60 to form a thin film having a more uniform film quality. Can do.
- FIG. 3 is a cross-sectional view showing the state of the atomic layer deposition apparatus 10 during the substrate carry-in process.
- the first opening 64 of the second container 60 is at a position facing the substrate loading / unloading port 28.
- substrate carrying in / out port 28 oppose be a 1st position. That is, in the substrate loading process, the second container 60 is in the first position.
- the second container 60 moves to the first position. This movement is performed by the control unit 100 controlling the first movement mechanism 36. Then, the shutter 27 is opened, and the substrate 12 is carried into the second container 60 through the shutter 27, the substrate loading / unloading port 28, and the first opening 64. As shown in FIG. 2B, the substrate is loaded by placing the substrate 12 on the fork 70 at the tip of the substrate placement of the transport carriage.
- FIG. 1 is a cross-sectional view showing the state of the atomic layer deposition apparatus 10 during the thin film formation process.
- the first opening 64 of the second container 60 is at a position facing the gas inlet 29.
- the position of the second container 60 in a state where the first opening 64 and the gas introduction port 29 face each other is referred to as a second position. That is, in the thin film forming process, the second container 60 is in the second position.
- the second container 60 moves to the second position. This movement is performed by the control unit 100 controlling the first moving mechanism 36.
- the pressing member 80 presses the second container 60 in the cylindrical longitudinal direction (horizontal direction) of the second container 60.
- the second internal space 62 is separated from the first internal space 22.
- a raw material gas is flowed from the gas introduction pipe 30 to the second internal space 62 to form a thin film on the substrate 12.
- FIG. 3 is a cross-sectional view showing the state of the atomic layer deposition apparatus 10 during the substrate unloading process.
- the second container 60 is in the first position.
- the pressing member 80 is pressing the second container 60 against the first container 20. Therefore, the pressing member 80 is moved in a direction in which the pressing member 80 moves away from the second container 60 (left direction in FIG. 1), and the pressing of the second container 60 is released.
- the second container 60 moves to the first position. This movement is performed by the control unit 100 controlling the first moving mechanism 36.
- the shutter 27 is opened, and the substrate 12 is unloaded from the second container 60 through the first opening 64, the substrate loading / unloading port 28, and the shutter 27.
- the substrate is unloaded by placing the substrate 12 on the fork portion 70 at the tip of the substrate placement of the transport carriage.
- the ALD apparatus 10 moves the second container 60 inside the first container 20 and has a simple structure as compared with the conventional technique, and the second internal space 62 and the substrate for forming a thin film. It is possible to separate the first internal space 22 that carries in and out. Therefore, the inner wall surface of the first container 20, the inner wall surface of the substrate loading / unloading port 28, and the inner wall surface of the shutter 27 are not exposed to the source gas, and particles are mixed when the substrate 12 is loaded and unloaded. Can be suppressed.
- FIG. 4 is a cross-sectional view showing the state of the atomic layer deposition apparatus 10 during the cleaning process.
- the lower portion 34 and the upper portion 40 of the first container 20 are separated.
- the second container 60 is taken out of the first container 20.
- the second moving mechanism 38 separates the lower part 34 including the bottom surface 32 of the first container 20 from the upper part 40 ( That is, the second container 60 moves to a position (third position) where the second container 60 can be taken out. This movement is performed by the control unit 100 controlling the second moving mechanism 38.
- the position where the second container 60 can be taken out means that the position in the height direction of the uppermost part of the second container 60 is lower than the position in the height direction of the lowermost part of the upper part 40 of the first container 20. It is such a position.
- the control unit 100 controls the first moving mechanism 36 so that the length of the support mechanism 36a is as short as possible. Thereby, the magnitude
- the first moving mechanism 36 is moved in the in-plane direction of the bottom surface 32 of the first container 20.
- the second container 60 can be moved from vertically below the upper portion 40 of the first container. In this way, the second container 60 is removed from the first container 20.
- the second container 60 provided inside the first container 20 can be easily taken out, the second container 60 can be easily cleaned.
- For cleaning for example, wet etching is performed.
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Abstract
Description
原子層堆積装置10は、TMA(Tri-Methyl-Aluminium)等の原料ガスと、オゾンO3等の酸化ガスを交互に供給して、原子単位で堆積して薄膜を形成する。
図1は、薄膜形成工程時における、基板12上に薄膜を形成する原子層堆積装置(以降、ALD装置という)10の概略の装置構成を示す断面図である。
以下、これらの構成について、より詳細に説明する。
まず、図1を参照して、第1の容器20について説明する。
第1の容器20は、SUS等の金属材料で構成されている。第1の容器20の上壁には、N2ガス(あるいは不活性ガス)を第1の内部空間22に導入するガス導入口が設けられている。また、第1の容器20の上壁には、排気管42が接続される排気口が設けられている。第1の内部空間22内のガスは、ターボ分子ポンプなどの排気部44により、第1の容器20の外部に排気される。これにより、第1の内部空間22内は、導入されたN2ガスの雰囲気で、所定の圧力に維持される。第1の内部空間22を所定の圧力に減圧することにより、後述するヒータ24、25が酸化するのを抑制することができる。
なお、基板12の搬入、搬出時の状態は、図3に示されている。図3についての説明は後述する。
また、第1の移動機構36はキャスタ37を備えており、第1の容器20の底面32の面内方向に移動することができる。
次に、図2を参照して、第2の容器60について説明する。図2(a)は、第2の容器60の概略構成図である。
第2の容器60は、第1の容器20の内部に設けられる。また、第2の容器60は、第2の内部空間62を形成する筒形状の容器である。第2の容器60は、安定した材質の点から石英が好適に用いられる。基板12をガラス基板とした場合、材料自体が略同じであるため、基板12に異なる成分が付着する心配がないという利点がある。
次に、図1を参照して、押え部材80について説明する。押え部材80は、第2の容器60を筒形状の長手方向(水平方向)に押える。押え部材80と第2の容器60との間には、Oリング86a、スペーサ84、Oリング86bが順に設けられている。また、第1の容器20の図1中左側の壁面と押え部材80との間には角型ベローズ82が設けられている。そのため、押え部材80は、水平方向に移動することができる。また、第2の容器60と第1の容器20の壁面26(図1中右側の面)との間には、Oリング90a、スペーサ88、Oリング90bが順に設けられている。また、ガス導入口29近傍の壁面26の内壁や、排気管68の内壁には、薄膜を形成すべき基板以外に薄膜が付着するのを防ぐための防着板31,83が設けられている。
次に、本実施形態の原子層堆積方法について説明する。
(基板搬入工程)
まず、基板搬入工程について説明する。図3は、基板搬入工程時における原子層堆積装置10の状態を示す断面図である。第2の容器60の第1の開口64は基板搬入出口28と対向する位置にある。以降、第1の開口64と基板搬入出口28とが対向する状態における第2の容器60の位置を第1の位置とする。すなわち、基板搬入工程では、第2の容器60は第1の位置にある。
そして、シャッタ27が開き、シャッタ27、基板搬入出口28、第1の開口64を通して、基板12が第2の容器60の内部に搬入される。基板の搬入は、図2(b)に示すように、搬送台車の基板載置先端のフォーク部70に基板12を載置して行う。
次に、薄膜形成工程について説明する。図1は、薄膜形成工程時における原子層堆積装置10の状態を示す断面図である。第2の容器60の第1の開口64はガス導入口29と対向する位置にある。以降、第1の開口64とガス導入口29とが対向する状態における第2の容器60の位置を第2の位置とする。すなわち、薄膜形成工程では、第2の容器60は第2の位置にある。
次に、基板搬出工程について説明する。図3は、基板搬出工程時における原子層堆積装置10の状態を示す断面図である。第2の容器60は第1の位置にある。
図4は、クリーニング工程時における原子層堆積装置10の状態を示す断面図である。第1の容器20の下側部分34と上側部分40とが分離した状態となっている。
12 基板
20 第1の容器
22 第1の内部空間
24,25 ヒータ
26 壁面
27 シャッタ
28 基板搬入出口
29 ガス導入口
30,30a,30b ガス導入管
31 防着板
32 底面
33 Oリング
34 下側部分
36 第1の移動機構
36a 支持機構
37 キャスタ
38 第2の移動機構
38a 支持機構
40 上側部分
42 排気管
44 排気部
60 第2の容器
62 第2の内部空間
64 第1の開口
66,66a,66b 第2の開口
67 基板支持部
68 排気管
69 排気部
70 フォーク部
80 固定部材
82 角型ベローズ
83 防着板
84,88 スペーサ
86a,86b,90a,90b Oリング
100 制御部
Claims (10)
- 基板上に薄膜を形成する原子層堆積装置であって、
第1の内部空間を形成する容器であって、基板を搬入又は搬出するための基板搬入出口と、基板上に薄膜を形成するガスを内部に導入するためのガス導入口とを異なる位置に備える第1の容器と、
前記第1の容器の内部に設けられ、前記第1の内部空間と隔てられる第2の内部空間を形成し、第1の開口を備える第2の容器と、
前記第2の容器を所定の方向に移動する第1の移動機構と、
基板を搬入又は搬出する場合、前記基板搬入出口と前記第1の開口とが対向する第1の位置に前記第2の容器を移動し、基板上に薄膜を形成する場合、前記ガス導入口と前記第1の開口とが対向する第2の位置に前記第2の容器を移動するように、前記第1の移動機構を制御する制御部と、
を有することを特徴とする原子層堆積装置。 - 前記基板搬入出口と前記ガス導入口とは、前記第1の容器の同じ壁面に設けられている、請求項1に記載の原子層堆積装置。
- 前記第2の容器は筒形状であり、前記第2の内部空間を前記第1の内部空間から隔てるために、筒形状の長手方向に該第2の容器を押える押え部材を備える、請求項1又は2のいずれかに記載の原子層堆積装置。
- 前記第2の容器は、前記第1の開口を備える側と反対側の端に、前記第2の内部空間内のガスが該第2の内部空間外に流れる第2の開口を備える、請求項3に記載の原子層堆積装置。
- 前記第1の容器は、該第1の容器の底面を含む下側部分と、該下側部分以外の上側部分とに分離可能に構成され、
前記原子層堆積装置は、前記下側部分を前記上側部分から分離するように移動する第2の移動機構を備え、
前記制御部は、前記第2の容器を前記第1の容器の外部に取り出す場合、前記第2の容器が外部に取り出せる位置である第3の位置に移動するように、前記第2の移動機構を制御する、請求項1乃至4のいずれかに記載の原子層堆積装置。 - 第1の内部空間を形成する第1の容器と、該第1の容器の内部に設けられ、該第1の内部空間と隔てられる第2の内部空間を形成する第2の容器とを用い、原子層堆積方法により基板上に薄膜を形成する薄膜形成方法であって、
前記第2の容器が備える第1の開口が、前記第1の容器が備える、基板を搬入又は搬出するための基板搬入出口と対向する第1の位置に移動し、基板を搬入する基板搬入工程と、
前記第1の開口が、前記第1の容器が備える、基板上に薄膜を形成するガスを前記第2の内部空間に導入するためのガス導入口と対向する第2の位置に移動し、薄膜を形成する薄膜形成工程と、
前記第1の開口が、前記基板搬入出口と対向する位置に移動し、基板を搬出する基板搬出工程と、
を有することを特徴とする薄膜形成方法。 - 前記ガス導入口は、前記基板搬入出口が設けられる壁面と同じ壁面に設けられ、前記ガス導入口を通して、基板上に薄膜を形成するガスを前記第2の内部空間に導入する、請求項6に記載の薄膜形成方法。
- 前記第2の容器は筒形状であり、
前記第2の内部空間を前記第1の内部空間から隔てるように、前記第2の容器の筒形状の長手方向に該第2の容器を押えて、前記第2の容器を前記第1の容器の内部で固定する工程を有する、請求項6又は7に記載の薄膜形成方法。 - 前記第2の容器が、前記第1の開口を備える側と反対側の端に備える第2の開口から、前記第2の内部空間内のガスを該第2の内部空間外に流す、請求項8に記載の薄膜形成方法。
- 前記第1の容器は、該第1の容器の底面を含む下側部分と、該下側部分以外の上側部分とに分離可能に構成され、
前記第2の容器を前記第1の容器の外部に取り出すために、前記第2の容器が外部に取り出せる位置である第3の位置に移動するように、前記下側部分を移動する工程を有する、請求項6乃至9のいずれかに記載の薄膜形成方法。
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US13/203,400 US9068261B2 (en) | 2009-03-10 | 2010-03-03 | Atomic layer deposition apparatus and thin film forming method |
EP10750510.9A EP2408003B1 (en) | 2009-03-10 | 2010-03-03 | Atomic layer deposition apparatus and thin film forming method |
KR1020117023449A KR101224975B1 (ko) | 2009-03-10 | 2010-03-03 | 원자층 퇴적 장치 및 박막 형성 방법 |
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JP (1) | JP4523661B1 (ja) |
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JP4523661B1 (ja) | 2010-08-11 |
EP2408003B1 (en) | 2014-09-24 |
JP2010212434A (ja) | 2010-09-24 |
EP2408003A1 (en) | 2012-01-18 |
EP2408003A4 (en) | 2013-08-14 |
TW201043726A (en) | 2010-12-16 |
US9068261B2 (en) | 2015-06-30 |
KR20110129453A (ko) | 2011-12-01 |
TWI500807B (zh) | 2015-09-21 |
US20110305836A1 (en) | 2011-12-15 |
KR101224975B1 (ko) | 2013-01-22 |
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