WO2013161768A1 - 成膜方法、成膜装置、及び、成膜システム - Google Patents
成膜方法、成膜装置、及び、成膜システム Download PDFInfo
- Publication number
- WO2013161768A1 WO2013161768A1 PCT/JP2013/061803 JP2013061803W WO2013161768A1 WO 2013161768 A1 WO2013161768 A1 WO 2013161768A1 JP 2013061803 W JP2013061803 W JP 2013061803W WO 2013161768 A1 WO2013161768 A1 WO 2013161768A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas
- film forming
- substrate
- plasma
- processed
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 94
- 239000007789 gas Substances 0.000 claims abstract description 311
- 239000002243 precursor Substances 0.000 claims abstract description 162
- 239000000758 substrate Substances 0.000 claims abstract description 158
- 238000012545 processing Methods 0.000 claims abstract description 107
- 239000002019 doping agent Substances 0.000 claims abstract description 56
- 239000004065 semiconductor Substances 0.000 claims abstract description 35
- 239000012495 reaction gas Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000009832 plasma treatment Methods 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 238000012546 transfer Methods 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 238000002347 injection Methods 0.000 description 44
- 239000007924 injection Substances 0.000 description 44
- 230000008569 process Effects 0.000 description 44
- 238000007789 sealing Methods 0.000 description 18
- 238000010926 purge Methods 0.000 description 17
- 238000000231 atomic layer deposition Methods 0.000 description 14
- 238000009792 diffusion process Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000011282 treatment Methods 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 7
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000002070 nanowire Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- -1 hydrogen ions Chemical class 0.000 description 4
- 238000002513 implantation Methods 0.000 description 4
- 238000010884 ion-beam technique Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000001902 propagating effect Effects 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CGRVKSPUKAFTBN-UHFFFAOYSA-N N-silylbutan-1-amine Chemical compound CCCCN[SiH3] CGRVKSPUKAFTBN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—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
- C23C16/511—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 using microwave discharges
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45536—Use of plasma, radiation or electromagnetic fields
- C23C16/4554—Plasma being used non-continuously in between ALD reactions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
- C23C16/45548—Atomic layer deposition [ALD] characterized by the apparatus having arrangements for gas injection at different locations of the reactor for each ALD half-reaction
- C23C16/45551—Atomic layer deposition [ALD] characterized by the apparatus having arrangements for gas injection at different locations of the reactor for each ALD half-reaction for relative movement of the substrate and the gas injectors or half-reaction reactor compartments
-
- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
- H01L21/02576—N-type
-
- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/0257—Doping during depositing
- H01L21/02573—Conductivity type
- H01L21/02579—P-type
-
- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
-
- 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 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
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/223—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a gaseous phase
- H01L21/2236—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a gaseous phase from or into a plasma phase
-
- 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 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
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
-
- 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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02524—Group 14 semiconducting materials
- H01L21/02532—Silicon, silicon germanium, germanium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/41—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions
- H01L29/423—Electrodes ; Multistep manufacturing processes therefor characterised by their shape, relative sizes or dispositions not carrying the current to be rectified, amplified or switched
- H01L29/42312—Gate electrodes for field effect devices
- H01L29/42316—Gate electrodes for field effect devices for field-effect transistors
- H01L29/4232—Gate electrodes for field effect devices for field-effect transistors with insulated gate
- H01L29/42384—Gate electrodes for field effect devices for field-effect transistors with insulated gate for thin film field effect transistors, e.g. characterised by the thickness or the shape of the insulator or the dimensions, the shape or the lay-out of the conductor
- H01L29/42392—Gate electrodes for field effect devices for field-effect transistors with insulated gate for thin film field effect transistors, e.g. characterised by the thickness or the shape of the insulator or the dimensions, the shape or the lay-out of the conductor fully surrounding the channel, e.g. gate-all-around
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
- H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
- H01L29/66409—Unipolar field-effect transistors
- H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
- H01L29/66787—Unipolar field-effect transistors with an insulated gate, i.e. MISFET with a gate at the side of the channel
- H01L29/66795—Unipolar field-effect transistors with an insulated gate, i.e. MISFET with a gate at the side of the channel with a horizontal current flow in a vertical sidewall of a semiconductor body, e.g. FinFET, MuGFET
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/78696—Thin film transistors, i.e. transistors with a channel being at least partly a thin film characterised by the structure of the channel, e.g. multichannel, transverse or longitudinal shape, length or width, doping structure, or the overlap or alignment between the channel and the gate, the source or the drain, or the contacting structure of the channel
Definitions
- Embodiments described herein relate generally to a film forming method, and a film forming apparatus and a film forming system that can be used for the implementation of the method, and more particularly, to a film formation of a layer containing a dopant. is there.
- MOSFET field effect transistor
- ions are formed in order to form a region having p-type or n-type conductivity, such as a source region, a drain region, and / or an extension region.
- Film formation and various plasma treatments and doping treatments are performed by an implantation apparatus, a plasma film formation apparatus, and a thermal CVD apparatus.
- a technique such as solid phase diffusion, ion beam implantation, or plasma doping is usually used for the doping process.
- a deposited film layer containing an element (dopant) to be doped on the substrate to be treated is formed by a CVD method, or the substrate to be treated is heated in a gas atmosphere containing the element to be doped.
- This is a technique for diffusing dopants.
- the ion beam implantation is a technique for implanting a dopant into a substrate to be processed using a relatively high energy ion beam.
- plasma doping is a technique in which dopant is directly injected into a substrate to be processed by generating a plasma of a gas containing the dopant and applying an RF bias to the substrate to be processed. It is.
- LSI large-scale integrated circuit semiconductor devices having a three-dimensional structure are attracting attention.
- MOSFETs development of fin-type or nanowire-type MOSFETs is in progress.
- the heating is generally performed at a very high temperature, the diffusion layer in the semiconductor device / LSI substrate becomes much larger than the desired depth (diffusion depth). Therefore, it cannot cope with the miniaturization of a semiconductor element that has been increasingly demanded in recent years.
- the ion diffusion direction cannot be controlled, the dopant may diffuse in the channel length direction, and the source region and the drain region may be connected.
- ion beam implantation and plasma doping since the dose of ions on the surface of a semiconductor substrate having a three-dimensional structure, that is, a plurality of concave and convex shapes having different directions, is different, uniform doping is performed on the plurality of surfaces. Is difficult.
- a film forming method is a step of (a) supplying a first precursor gas of a semiconductor material into a processing container in which a substrate to be processed is disposed. Adsorbing the gas to the substrate to be processed; and (b) supplying the second precursor gas of the dopant material into the processing container, and adsorbing the second precursor gas to the substrate to be processed.
- This step includes (c) a step of generating plasma of a reactive gas in a processing container, and performing the plasma processing so as to modify the layer adsorbed on the substrate to be processed.
- the plasma may be excited by microwaves.
- the first precursor gas and the second precursor gas are adsorbed on the substrate to be processed by the ALD (Atomic Layer Deposition) method, and then the atomic adsorption layer of the dopant adsorbed on the substrate to be processed is plasma-treated. Modification by treatment. Therefore, according to this method, it is possible to form a film containing a dopant uniformly and conformally on a surface having a three-dimensional structure, that is, a plurality of surfaces having different directions. Note that conformal indicates a state where the surface having a three-dimensional structure is uniformly doped without uneven concentration.
- the step of supplying the first precursor gas and the step of supplying the second precursor gas may be performed separately.
- the ratio of the number of executions of the step of supplying the first precursor gas to the number of executions of the step of supplying the second precursor gas depends on the ratio of the dopant contained in the film formed on the substrate to be processed. The density can be adjusted.
- the step of generating plasma includes a step of performing a first plasma process and a step of performing a second plasma process.
- the first precursor gas is used.
- the layer adsorbed on the substrate to be processed in the supplying step is subjected to plasma processing using reactive gas plasma.
- the substrate to be processed is supplied by supplying the second precursor gas. Plasma treatment may be performed on the layer adsorbed on the substrate.
- the first precursor gas and the second precursor gas each further include one or more of hydrogen atoms and chlorine atoms, and performing the first plasma treatment and the second plasma.
- plasma of hydrogen gas that is a reaction gas may be excited.
- impurities other than the dopant can be removed from the layer adsorbed on the substrate to be processed by a reduction reaction using hydrogen.
- the process of supplying the first precursor gas and the process of supplying the second precursor gas are performed simultaneously, whereby the first precursor gas and the second precursor gas are applied to the substrate to be processed.
- a mixed gas of the precursor gas may be adsorbed.
- the concentration of the dopant contained in the film formed on the substrate to be processed can be adjusted by the ratio between the flow rate of the first precursor gas and the flow rate of the second precursor gas.
- the first precursor gas and the second precursor gas each further include one or more of hydrogen atoms and chlorine atoms, and in the step of performing plasma treatment, plasma of hydrogen gas that is a reactive gas is used. May be excited.
- impurities other than the desired dopant can be removed from the layer adsorbed on the substrate to be processed by a reduction reaction using hydrogen.
- the film forming method includes a series of steps including the step of adsorbing the first precursor gas, the step of adsorbing the second precursor gas, and the step of generating plasma one or more times. After the repetition, a step of annealing the substrate to be processed may be further included. According to this embodiment, the film formed on the substrate to be processed can be activated by annealing the substrate to be processed.
- the film forming method according to an embodiment may further include a step of forming a cap layer on the surface of the film formed on the substrate to be processed before the step of annealing the substrate to be processed. According to this embodiment, it becomes possible to perform annealing while protecting the film formed by the above-described series of steps, and as a result, dopant contained in the film is diffused out of the film by annealing. It is possible to suppress a decrease in the dopant concentration.
- a film forming apparatus includes a processing container, a supply unit, and a plasma generation unit.
- a substrate to be processed is disposed in the processing container.
- the supply unit includes the first precursor gas and the second precursor in the processing container so that the first precursor gas of the semiconductor material and the second precursor gas of the dopant material are adsorbed to the substrate to be processed.
- the plasma generation unit generates plasma of a reactive gas in the processing container so as to modify the layer adsorbed on the substrate to be processed by plasma processing.
- the plasma generation unit may use plasma excited by microwaves.
- the first precursor gas and the second precursor gas are adsorbed on the substrate to be processed by an ALD (Atomic Layer Deposition) method, and the layer adsorbed on the substrate to be processed is modified by plasma treatment.
- ALD Atomic Layer Deposition
- plasma treatment Can be intended. Therefore, according to this film forming apparatus, a film containing a dopant can be formed uniformly and conformally on the surface of the semiconductor substrate having a three-dimensional structure.
- the film forming apparatus may further include a control unit that controls the supply unit and the plasma generation unit.
- control unit (a) controls the supply unit to supply the first precursor gas into the processing container, and (b) adsorbs to the substrate to be processed by supplying the first precursor gas. (C) controlling the supply unit to supply the second precursor gas into the processing container; and (c) d)
- the plasma generation unit may be controlled so as to generate plasma of a reactive gas in order to perform plasma processing on the layer adsorbed on the substrate to be processed by supplying the second gas.
- concentration of the dopant contained in the film formed on the substrate to be processed is adjusted by the ratio between the number of times of supplying the first precursor gas and the number of times of supplying the second precursor gas. be able to.
- the supply unit may supply a mixed gas of the first precursor gas and the second precursor gas into the processing container, and the control unit supplies the mixed gas into the processing container.
- the supply unit may be controlled so that the plasma generation unit may be controlled so as to generate plasma of a reactive gas in order to perform plasma processing on the layer adsorbed on the substrate to be processed by supplying the mixed gas.
- the concentration of the dopant contained in the film formed on the substrate to be processed can be adjusted by the ratio between the flow rate of the first precursor gas and the flow rate of the second precursor gas.
- each of the first gas and the second gas may further include one or more of hydrogen atoms and chlorine atoms, and the plasma generation unit may generate a plasma of hydrogen gas that is a reaction gas.
- impurities other than the dopant can be removed from the layer adsorbed on the substrate to be processed by a reduction reaction using hydrogen.
- a film forming system is a doping system using ALD film forming, and the film forming apparatus according to any one of the above-described aspects or embodiments and a target to be processed by the film forming apparatus.
- An annealing apparatus that receives the substrate and anneals the substrate to be processed is provided. According to this film forming system, it is possible to activate the film formed on the substrate to be processed by annealing the substrate to be processed.
- the film forming system may further include a film forming apparatus of a doping system using another ALD film forming, and the other ALD film forming apparatus is provided via a film forming apparatus and a vacuum transfer system.
- the cap substrate may be formed on the surface of the substrate to be processed by receiving the substrate to be processed from the film forming apparatus, and the annealing apparatus is connected to the other film forming apparatus and is connected to the other substrate.
- the substrate to be processed conveyed from the film apparatus may be annealed. According to this embodiment, it is possible to perform annealing while protecting the film formed on the substrate to be processed, and as a result, it is possible to prevent the dopant contained in the film from leaving the film. It becomes.
- a film containing a dopant can be formed to follow a three-dimensional surface with high uniformity.
- FIG. 1 is a plan view schematically showing a film forming system according to an embodiment. It is sectional drawing of the film-forming apparatus which concerns on one Embodiment. 1 is a top view schematically showing a film forming apparatus according to an embodiment. It is a top view which shows the state which removed the upper part of the processing container from the film-forming apparatus shown in FIG.
- FIG. 3 is an enlarged cross-sectional view of a part of the film forming apparatus shown in FIG. 2, and shows a cross section that crosses a portion including a region R1 in parallel with the axis X. It is the top view which looked at the injection part of the gas supply part 16 of the film-forming apparatus shown in FIG.
- FIG. 11 is a cross-sectional view taken along line XI-XI in FIG. 10.
- FIG. 1 is a plan view schematically showing a film forming system according to an embodiment.
- a film forming system 100 shown in FIG. 1 includes mounting tables 102a to 102d, storage containers 104a to 104d, a loader module LM, load lock chambers LL1 and LL2, process modules PM1, PM2, PM3, and a transfer chamber 110. .
- the mounting tables 102a to 102d are arranged along one edge of the loader module LM.
- the containers 104a to 104d are mounted on the mounting tables 102a to 102d, respectively.
- a substrate to be processed W is accommodated in the accommodating containers 104a to 104d.
- the transfer robot Rb1 is provided in the loader module LM.
- the transfer robot Rb1 takes out the substrate to be processed W stored in any of the storage containers 104a to 104d, and transfers the substrate to be processed W to the load lock chamber LL1 or LL2.
- the load lock chambers LL1 and LL2 are provided along another edge of the loader module LM and constitute a preliminary decompression chamber.
- the load lock chambers LL1 and LL2 are connected to the transfer chamber 110 via gate valves, respectively.
- the transfer chamber 110 is a depressurizable chamber, and another transfer robot Rb2 is provided in the chamber.
- Process modules PM1 to PM3 are connected to the transfer chamber 110 through corresponding gate valves.
- the transfer robot Rb2 takes out the substrate W to be processed from the load lock chamber LL1 or LL2, and sequentially transfers it to the process modules PM1, PM2, and PM3.
- Each of the process modules PM1, PM2, and PM3 of the film forming system 100 may be a film forming apparatus, another film forming apparatus, and an annealing apparatus according to an embodiment.
- FIG. 2 is a cross-sectional view of a film forming apparatus according to an embodiment.
- FIG. 3 is a top view schematically showing a film forming apparatus according to an embodiment.
- FIG. 2 shows a cross section taken along the line II-II in FIG. 4 is a plan view showing a state in which the upper portion of the processing container is removed from the film forming apparatus shown in FIG.
- a film forming apparatus 10 shown in FIGS. 2 to 4 is a so-called semi-batch type film forming apparatus, and is an apparatus for forming a film by the ALD method.
- the film forming apparatus 10 includes a processing container 12, a mounting table 14, a gas supply unit 16, an exhaust unit 18, a gas supply unit 20, and a plasma generation unit 22.
- the processing container 12 is a substantially cylindrical container extending in the axis X direction.
- the processing container 12 defines a processing chamber C therein.
- the processing container 12 may be made of, for example, a metal such as aluminum whose inner surface is subjected to plasma resistance processing (for example, alumite processing or Y 2 O 3 spraying processing).
- the processing vessel 12 includes a lower portion 12a and an upper portion 12b.
- the lower portion 12a has a cylindrical shape that opens upward, and includes a side wall and a bottom wall that define the processing chamber C.
- the upper part 12b is a lid that defines the processing chamber C from above.
- the upper part 12b is attached to the top of the lower part 12a so as to close the upper opening of the lower part 12a.
- An elastic sealing member for sealing the processing chamber C may be provided between the lower portion 12a and the upper portion 12b.
- a mounting table 14 is provided in the processing chamber C defined by the processing container 12.
- the mounting table 14 has a substantially disk shape.
- the mounting table 14 is configured to be rotatable about the axis X.
- the mounting table 14 is rotationally driven about the axis X by the drive mechanism 24.
- the driving mechanism 24 includes a driving device 24 a such as a motor and a rotating shaft 24 b, and is attached to the lower portion 12 a of the processing container 12.
- the rotating shaft 24b extends into the processing chamber C with the axis X as the central axis, and rotates about the axis X by the driving force from the driving device 24a.
- the central portion of the mounting table 14 is supported on the rotating shaft 24b. Thereby, the mounting table 14 is rotated about the axis X.
- an elastic sealing member such as an O-ring may be provided between the lower portion 12 a of the processing container 12 and the driving mechanism 24 so as to seal the processing chamber C.
- one or more placement areas 14 a are provided on the top surface of the placement table 14.
- the plurality of placement areas 14 a are arranged in the circumferential direction with respect to the axis X.
- the placement region 14a is configured as a recess having a diameter that is substantially the same as the diameter of the substrate to be processed W placed in the region or slightly larger than the diameter of the substrate to be processed W.
- a heater 26 for heating the substrate to be processed W placed on the placement region 14 a is provided below the placement table 14.
- the substrate W to be processed is transferred to the processing chamber C by the transfer robot via the gate valve G provided in the processing container 12, and is mounted on the mounting region 14a.
- the processing chamber C includes a first region R1 and a second region R2 arranged in the circumferential direction with respect to the axis X. Therefore, the to-be-processed base
- FIG. 5 is an enlarged cross-sectional view of a part of the film forming apparatus shown in FIG. 2, and shows a cross section that crosses a portion including the region R1 in parallel with the axis X.
- FIG. 6 is a plan view of the injection unit of the gas supply unit 16, the exhaust port of the exhaust unit 18, and the injection port of the gas supply unit 20 of the film forming apparatus shown in FIG. 2 as viewed from below, that is, from the mounting table side. is there.
- an injection unit 16a of the gas supply unit 16 is provided above the first region R1 so as to face the upper surface of the mounting table.
- the region facing the injection unit 16a among the regions included in the processing chamber C is the first region R1.
- the injection part 16a is formed with a plurality of injection ports 16h.
- the gas supply unit 16 supplies the precursor gas to the first region R1 from the plurality of injection ports 16h. By supplying the precursor gas to the first region R1, the precursor gas is chemically adsorbed on the surface of the substrate to be processed W that passes through the first region R1.
- the precursor gas supplied from the injection unit 16a to the first region R1 includes a first precursor gas and a second precursor gas.
- the first precursor gas is a precursor gas of a semiconductor material.
- the first precursor gas can include silicon as a semiconductor material, and can further include at least one of chlorine atoms and hydrogen atoms.
- Such first precursor gas is, for example, DCS (dichlorosilane).
- the second precursor gas is a dopant material precursor gas.
- the second precursor gas can contain arsenic or phosphorus as the n-type dopant material, and can further contain at least one of chlorine atoms and hydrogen atoms.
- Such a second precursor gas is, for example, AsClH 2 gas.
- the second precursor gas can contain boron as the p-type dopant material, and can further contain at least one of chlorine atoms and hydrogen atoms.
- a second precursor gas is, for example, B (CH 3 ) 2 H gas.
- the first precursor gas and the second precursor gas may be switched and supplied from the injection unit 16a, or a mixed gas of the first and second precursor gases may be supplied. Good.
- the edge part which defines the injection part 16a includes the two edge parts 16e which define the said injection part 16a from the circumferential direction. These two edge portions 16e extend so as to approach each other as they approach the axis X.
- the two edges 16e may extend in the radial direction with respect to the axis X, for example. That is, the injection part 16a may have a substantially fan-shaped planar shape.
- the plurality of injection ports 16h are provided between the two edge portions 16e.
- the speed of each position in the substrate W to be processed accompanying the rotation of the mounting table 14 varies depending on the distance from the axis X. That is, as the position is farther from the axis X, the speed increases.
- the injection unit 16a is configured to face more injection ports 16h as the position in the substrate W to be processed is farther from the axis X. Therefore, variations in time during which each position of the substrate to be processed W is exposed to the precursor gas can be reduced.
- an exhaust port 18a is provided around the injection unit 16a, and the exhaust unit 18 exhausts the first region R1 from the exhaust port 18a.
- the exhaust port 18a of the exhaust unit 18 faces the upper surface of the mounting table 14, and extends along a closed path surrounding the outer periphery of the injection unit 16a as shown in FIG.
- the narrow exhaust port 18a surrounds the periphery of the injection unit 16a.
- an injection port 20a of a gas supply unit 20 is provided around the exhaust port 18a, and the gas supply unit 20 injects a purge gas from the injection port 20a.
- the injection port 20a of the gas supply unit 20 faces the upper surface of the mounting table 14, and extends along a closed path surrounding the outer periphery of the exhaust port 18a.
- an inert gas such as Ar gas or N 2 gas can be used.
- the precursor gas supplied to the first region R1 is prevented from leaking out of the first region R1 due to the exhaust from the exhaust port 18a and the injection of the purge gas from the injection port 20a.
- the reactive gas or the radical thereof supplied in the second region R2 is suppressed from entering the first region R1, as will be described later.
- the exhaust unit 18 and the gas supply unit 20 separate the first region R1 and the second region R2.
- the injection port 20a and the exhaust port 18a have a belt-like planar shape extending along a closed path surrounding the outer periphery of the injection unit 16a, the width of each of the injection port 20a and the exhaust port 18a is narrowed. Yes.
- the width W2 of the exhaust port 18a and the width W3 (see FIG. 6) of the injection port 20a extending between the first region R1 and the second region R2 are set in the placement region 14a. Is smaller than the diameter W1 (see FIG. 4).
- the film forming apparatus 10 may include a unit U that defines the injection unit 16a, the exhaust port 18a, and the injection port 20a.
- FIG. 7 and FIG. 8 are also referred to.
- FIG. 7 is an exploded perspective view of a unit according to an embodiment that defines the injection unit 16a, the exhaust port 18a, and the injection port 20a.
- FIG. 8 is a plan view of the unit shown in FIG. 7 as viewed from above.
- FIG. 8 shows the upper surface of the unit U
- FIG. 6 shows the lower surface of the unit U.
- the unit U is composed of a first member M1, a second member M2, a third member M3, and a fourth member M4.
- the members M1 to M4 are stacked in order from the top.
- the unit U is attached to the processing container 12 so as to contact the lower surface of the upper part 12b of the processing container 12, and the elastic sealing member 30 is provided between the lower surface of the upper part 12b of the processing container 12 and the first member M1. Is provided.
- the elastic sealing member 30 extends along the outer edge of the upper surface of the first member M1.
- the first to fourth members M1 to M4 have a substantially fan-shaped planar shape.
- the first member M1 defines, on the lower side thereof, a recess in which the second to fourth members M2 to M4 are accommodated.
- the second member M2 defines, on the lower side thereof, a recess for accommodating the third to fourth members M3 to M4.
- the third member M3 and the fourth member M4 have substantially the same planar size.
- a gas supply path 16p penetrating the first to third members M1 to M3 is formed.
- the gas supply path 16p is connected at its upper end to a gas supply path 12p provided in the upper part 12b of the processing container 12.
- a gas source 16g of a first precursor gas is connected to the gas supply path 12p via a flow rate controller 16c such as a valve 16v and a mass flow controller.
- a gas source 17g of a second precursor gas is connected to the gas supply path 12p via a flow rate controller 17c such as a valve 17v and a mass flow controller.
- the lower end of the gas supply path 16p is connected to a space 16d formed between the third member M3 and the fourth member M4.
- the space 16d is connected to an injection port 16h of the injection unit 16a provided in the fourth member M4.
- an elastic sealing member 32a such as an O-ring is provided so as to surround a connecting portion between the gas supply path 12p and the gas supply path 16p.
- the elastic sealing member 32a can prevent the precursor gas supplied to the gas supply path 16p and the gas supply path 12p from leaking from the boundary between the upper portion 12b of the processing container 12 and the first member M1.
- an elastic sealing member such as an O-ring is provided between the first member M1 and the second member M2 and between the second member M2 and the third member M3 so as to surround the gas supply path 16p.
- 32b and 32c are provided, respectively.
- the precursor gas supplied to the gas supply path 16p by the elastic sealing members 32b and 32c is the boundary between the first member M1 and the second member M2, and the boundary between the second member M2 and the third member M3. Leaking from can be prevented.
- An elastic sealing member 32d is provided between the third member M3 and the fourth member M4 so as to surround the space 16d. The elastic sealing member 32d can prevent the precursor gas supplied to the space 16d from leaking from the boundary between the third member M3 and the fourth member M4.
- an exhaust passage 18q that penetrates the first and second members M1 and M2 is formed.
- the exhaust path 18q is connected at its upper end to an exhaust path 12q provided in the upper part 12b of the processing container 12.
- the exhaust path 12q is connected to an exhaust device 34 such as a vacuum pump.
- the exhaust path 18q is connected to a space 18d provided at the lower end between the lower surface of the second member M2 and the upper surface of the third member M3.
- the second member M2 defines a recess that accommodates the third member M3 and the fourth member M4, and the inner surface of the second member M2 that defines the recess and the second member M2
- a gap 18g is provided between the side end surfaces of the third member M3 and the fourth member M4.
- the space 18d is connected to the gap 18g.
- the lower end of the gap 18g functions as the exhaust port 18a described above.
- an elastic sealing member 36a such as an O-ring is provided so as to surround a connection portion between the exhaust path 18q and the exhaust path 12q.
- the elastic sealing member 36a can prevent the exhaust gas passing through the exhaust passage 18q and the exhaust passage 12q from leaking from the boundary between the upper portion 12b of the processing container 12 and the first member M1.
- an elastic sealing member 36b such as an O-ring is provided between the first member M1 and the second member M2 so as to surround the exhaust passage 18q.
- the elastic sealing member 36b can prevent the gas passing through the exhaust path 18q from leaking from the boundary between the first member M1 and the second member M2.
- a gas supply path 20r penetrating the first member M1 is formed.
- the gas supply path 20r is connected at its upper end to a gas supply path 12r provided in the upper part 12b of the processing container 12.
- a gas source 20g of purge gas is connected to the gas supply path 12r via a flow rate controller 20c such as a valve 20v and a mass flow controller.
- the lower end of the gas supply path 20r is connected to a space 20d provided between the lower surface of the first member M1 and the upper surface of the second member M2.
- the first member M1 defines a recess that accommodates the second to fourth members M2 to M4, and the inner surface of the first member M1 that defines the recess and the first member M1.
- a gap 20p is provided between the side surfaces of the second member M2. This gap 20p is connected to the space 20d. Further, the lower end of the gap 20p functions as the injection port 20a of the gas supply unit 20.
- an elastic sealing member 38 such as an O-ring is provided so as to surround a connection portion between the gas supply path 12r and the gas supply path 20r. The elastic sealing member 38 prevents the purge gas passing through the gas supply path 20r and the gas supply path 12r from leaking from the boundary between the upper part 12b and the first member M1.
- FIG. 9 is an enlarged cross-sectional view of the film forming apparatus shown in FIG. 2, and is an enlarged cross-sectional view of a portion where a plasma generation unit is provided.
- the film forming apparatus 10 includes a plasma generation unit 22.
- the plasma generator 22 supplies a reactive gas to the second region R2 and supplies a microwave to the second region R2, thereby generating a plasma of the reactive gas in the second region R2, and a substrate to be processed.
- Plasma treatment is performed on the precursor gas layer adsorbed on W.
- the precursor gas chemisorbed on the substrate W to be processed that is, the precursor gas layer
- a reaction gas for example, H 2 gas can be used.
- the plasma generation unit 22 may include one or more antennas 22a for supplying microwaves to the second region R2.
- Each of the one or more antennas 22a may include a dielectric plate 40 and one or more waveguides.
- the four antennas 22 a are arranged in the circumferential direction with respect to the axis X.
- Each antenna 22a includes a dielectric plate 40 provided above the second region R2 and a waveguide 42 provided on the dielectric plate 40.
- FIG. 10 is a plan view showing one antenna of the film forming apparatus according to the embodiment as viewed from above.
- FIG. 11 is a cross-sectional view taken along the line XI-XI in FIG.
- the dielectric plate 40 is a substantially plate-like member made of a dielectric material such as quartz.
- the dielectric plate 40 is provided so as to face the second region R2, and is supported by the upper portion 12b of the processing container 12.
- an opening AP is formed in the upper portion 12b of the processing container 12 so that the dielectric plate 40 is exposed to the second region R2.
- the plane size of the upper portion of the opening AP (size in the plane intersecting the axis X) is larger than the plane size of the lower portion of the opening AP (size in the plane intersecting the axis X).
- the upper surface 12b that defines the opening AP is provided with a step surface 12s facing upward.
- the edge portion of the dielectric plate 40 functions as the supported portion 40s and abuts on the step surface 12s.
- the dielectric plate 40 is supported by the upper portion 12b when the supported portion 40s contacts the step surface 12s.
- An elastic sealing member may be provided between the step surface 12s and the dielectric plate 40.
- the dielectric plate 40 supported by the upper portion 12b faces the mounting table 14 via the second region R2.
- a portion exposed from the opening AP of the upper portion 12b that is, a portion facing the second region R2 functions as a dielectric window 40w.
- the edge of the dielectric window 40w includes two edges 40e that approach each other as the axis X is approached. Due to the shape of the dielectric window 40w, that is, the shape in which the length in the circumferential direction increases as the distance from the axis X increases, variations in time during which each position of the substrate to be processed W is exposed to the plasma of the reaction gas can be reduced.
- the planar shape of the dielectric plate 40 including the dielectric window 40w and the supported portion 40s may be a substantially fan shape, or may be a polygonal shape so that the processing is easy.
- a waveguide 42 is provided on the dielectric plate 40.
- the waveguide 42 is a rectangular waveguide, and is disposed on the dielectric plate 40 so that the internal space 42 i in which the microwave propagates extends in a substantially radial direction with respect to the axis X above the dielectric window 40 w. Is provided.
- the waveguide 42 may include a slot plate 42a, an upper member 42b, and an end member 42c.
- the slot plate 42a is a metal plate-like member, and defines an internal space 42i of the waveguide 42 from below.
- the slot plate 42 a is in contact with the upper surface of the dielectric plate 40 and covers the upper surface of the dielectric plate 40.
- the slot plate 42a has a plurality of slot holes 42s in a portion that defines the internal space 42i.
- a metal upper member 42b is provided on the slot plate 42a so as to cover the slot plate 42a.
- the upper member 42b defines an internal space 42i of the waveguide 42 from above.
- the upper member 42b can be screwed to the upper portion 12b so that the slot plate 42a and the dielectric plate 40 are sandwiched between the upper member 42b and the upper portion 12b of the processing container 12.
- the end member 42 c is a metal member and is provided at one end of the waveguide 42 in the longitudinal direction. That is, the end member 42c is attached to one end of the slot plate 42a and the upper member 42b so as to close one end of the internal space 42i.
- a microwave generator 48 is connected to the other end of the waveguide 42.
- the microwave generator 48 generates a microwave of about 2.45 GHz and supplies the microwave to the waveguide 42.
- the microwave generated by the microwave generator 48 and propagating through the waveguide 42 is supplied to the dielectric plate 40 through the slot hole 42s of the slot plate 42a, and is supplied to the second region via the dielectric window 40w. Supplied to R2.
- the microwave generator 48 may be common to the plurality of waveguides 42.
- a plurality of microwave generators 48 may be connected to the plurality of waveguides 42, respectively. In this way, by using one or more microwave generators 48 connected to the plurality of antennas 22a, and adjusting the intensity of the microwaves generated by the microwave generators 48, the microwaves applied to the second region R2 It is possible to increase the strength.
- generation part 22 contains the gas supply part 22b.
- the gas supply unit 22b supplies the reaction gas to the second region R2.
- This reaction gas is for modifying the layer of the precursor gas chemically adsorbed on the substrate to be processed W as described above, and may be, for example, H 2 gas.
- the gas supply part 22b may include a gas supply path 50a and an injection port 50b.
- the gas supply path 50a is formed in the upper part 12b of the processing container 12 so as to extend around the opening AP.
- an injection port 50b for injecting the reactive gas supplied to the gas supply path 50a toward the lower side of the dielectric window 40w is formed in the upper portion 12b of the processing container 12.
- a plurality of injection ports 50b may be provided around the opening AP.
- a gas source 50g of a reaction gas is connected to the gas supply path 50a via a flow rate controller 50c such as a valve 50v and a mass flow controller.
- the reactive gas is supplied to the second region R2 by the gas supply unit 22b, and the microwave is supplied to the second region R2 by the antenna 22a.
- plasma of the reactive gas is generated in the second region R2.
- the second region R2 is a region where plasma of the reactive gas is generated.
- the angle range in which the second region R2 extends in the circumferential direction with respect to the axis X is larger than the angle range in which the first region R1 extends in the circumferential direction.
- the layer of the precursor gas chemically adsorbed on the substrate W to be processed is modified by the plasma of the reaction gas generated in the second region R2.
- an exhaust port 22 h is formed in the lower portion 12 a of the processing container 12 below the outer edge of the mounting table 14.
- An exhaust device 52 shown in FIG. 9 is connected to the exhaust port 22h.
- the film forming apparatus 10 may further include a control unit 60 for controlling each element of the film forming apparatus 10.
- the control unit 60 may be a computer including a CPU (Central Processing Unit), a memory, an input device, and the like.
- each element of the film forming apparatus 10 can be controlled by the CPU operating in accordance with a program stored in the memory.
- the control unit 60 sends a control signal to the driving device 24a to control the rotation speed of the mounting table 14, and a power source connected to the heater 26 to control the temperature of the substrate W to be processed.
- a control signal is sent to the flow rate controller 17c, a control signal is sent to the exhaust device 34 in order to control the exhaust amount of the exhaust device 34 connected to the exhaust port 18a, and a valve 20v and A control signal is sent to the flow controller 20c, a control signal is sent to the microwave generator 48 to control the power of the microwave, and a valve 50v and a flow controller 50c are controlled to control the flow rate of the reaction gas.
- Sends a control signal it can send a control signal to the exhaust system 52 to control the exhaust amount of the exhaust device 52.
- the film forming apparatus 10 chemically adsorbs the first precursor gas on the surface of the substrate to be processed W in the first region R1, and the first precursor gas adsorbed on the substrate to be processed W in the second region R2.
- These layers can be modified by reactive gas plasma.
- the first precursor gas is DCS
- chlorine is extracted from the DCS layer chemically adsorbed on the surface of the substrate W to be processed by a reduction reaction using hydrogen gas plasma, and a silicon atom film is processed. It can be formed on the surface of the substrate W.
- the film forming apparatus 10 chemically adsorbs the second precursor gas on the surface of the substrate to be processed W in the first region R1, and the second precursor adsorbed on the substrate to be processed W in the second region R2.
- the gas layer can be modified by the plasma of the reaction gas.
- the second precursor gas is AsClH 2 gas
- chlorine is extracted from the layer of AsClH 2 gas chemically adsorbed on the surface of the substrate W to be processed by a reduction reaction by hydrogen gas plasma, and As atoms A layer can be formed on the surface of the substrate W to be processed.
- the pressure in the second region R2 is preferably 1 Torr (133.3 Pa) or more.
- the pressure in the second region R2 is preferably 1 Torr (133.3 Pa) to 50 Torr (6666 Pa), and more preferably 1 Torr (133.3 Pa) to 10 Torr (1333 Pa).
- the gas supplied to the first region R1 is the first precursor gas and the second gas.
- the precursor gas can be selected. Therefore, in the film forming apparatus 10, the ratio of the number of times of supplying the first precursor gas to the first region R1 and the number of times of supplying the second precursor gas to the first region R1 is adjusted to adjust the ratio. The concentration of the dopant in the film formed on the processing substrate W can be adjusted.
- the film forming apparatus 10 can supply a mixed gas of the first precursor gas and the second precursor gas to the first region R1.
- the concentration of the dopant in the film formed on the substrate to be processed W is adjusted by adjusting the ratio of the flow rate of the first precursor gas to the flow rate of the second precursor gas in the mixed gas. be able to.
- FIG. 12 is a perspective view showing an example of a semiconductor device that can use the film forming apparatus of one embodiment in its manufacturing process.
- a semiconductor device D10 shown in FIG. 12 is a fin-type MOS transistor.
- the semiconductor device D10 includes a substrate D12, an insulating film D14, a fin D16, a gate insulating film D18, and a gate electrode D20.
- the insulating film D14 is provided on the substrate D12.
- the fin D16 has a substantially rectangular parallelepiped shape and is provided on the insulating film D14.
- the gate insulating film D18 is provided so as to cover a side surface and an upper surface of a part of the fin D16.
- the gate electrode D20 is provided on the gate insulating film D18.
- extended regions E10 and E12 including a low-concentration dopant are formed in the fin D16 on both sides of the gate insulating film D18. Further, in the semiconductor device D10, the source region Sr10 and the drain region Dr10 including a high concentration dopant are further formed in the fin D16 adjacent to the extension regions E10 and E12.
- the fin D16 of the semiconductor device D10 has a three-dimensional shape, that is, an upper surface and side surfaces as shown in FIG. Since the film formation apparatus 10 can perform film formation based on the ALD method, it can also form a film on such a three-dimensional shape, that is, the upper surface and the side surface. Therefore, according to the film forming apparatus 10, it is possible to form the extended region, the source region, and the drain region having a uniform film thickness on the side surface and the upper surface of the fin D16.
- the film forming apparatus 10 can be suitably used for manufacturing the semiconductor device D30 shown in FIG. 13 in addition to the fin-type MOS transistor.
- a semiconductor device D30 illustrated in FIG. 13 is a nanowire-type MOS transistor, and includes a substantially columnar nanowire portion D32 instead of the fin D16 of the semiconductor device D10 described above.
- the gate insulating film D18 is formed so as to cover the entire surface of a part of the nanowire portion D32 in the longitudinal direction, and the gate electrode D20 is formed so as to cover the gate insulating film D18.
- extended regions are formed in the nanowire portion D32 on both sides of the gate insulating film, and a source region and a drain region are formed on the sides of the extended region.
- the film forming apparatus 10 it is possible to form the extended region, the source region Sr10, and the drain region Dr10 having a uniform film thickness over the three-dimensional surface of the nanowire part D32.
- the film forming apparatus 10 can also be used for forming the extension region, the source region, and the drain region of the planar type MOS transistor.
- the process module PM2 receives the substrate W to be processed which is transferred by the transfer robot Rb2 after the film formation by the film forming apparatus 10 is performed.
- the process module PM2 forms a cap layer on the surface of the substrate to be processed W.
- the cap layer may be, for example, a SiN film, and can prevent the dopant from detaching from the film by annealing described later.
- the process module PM2 may have a configuration similar to that of the film forming apparatus 10 in one embodiment.
- the process module PM2 supplies a silicon precursor gas, for example, BTBAS (Bistal Butylaminosilane), to the first region R1, and nitrogen gas (N 2 gas) or NH in the second region R2.
- a silicon precursor gas for example, BTBAS (Bistal Butylaminosilane)
- N 2 gas nitrogen gas
- Three gas plasma can be generated.
- the target substrate W provided with the cap layer by the process module PM2 is transferred to the process module PM3 by the transfer robot Rb2.
- the process module PM3 is an annealing apparatus according to an embodiment. As the annealing apparatus, it is desirable to use a lamp annealer having general lamp heating or a microwave annealing apparatus using microwaves.
- the process module PM3 performs an annealing process on the substrate to be processed W accommodated therein. Thereby, the process module PM3 activates the film containing the dopant formed on the substrate to be processed W.
- the process module PM3 may heat the substrate W to be processed at a temperature of 1050 ° C. for about 1 second in an N 2 gas atmosphere.
- the heating time of this annealing treatment is considerably shorter than the heating treatment time used in normal solid phase diffusion, for example, preferably 0.1 to 10 seconds, and preferably 0.5 to 5 seconds. More preferred. Therefore, excessive diffusion of the dopant can be suppressed. For example, it is possible to suppress dopant diffusion in the channel length direction of a semiconductor device / LSI large-scale integrated circuit.
- FIG. 14 is a flowchart showing a film forming method according to an embodiment.
- the substrate W to be processed is transferred to the process module PM1, that is, the film forming apparatus 10 in step S1.
- the film forming apparatus 10 film formation including steps S2 to S8 is performed.
- steps S2 to S8 the substrate W to be processed is heated to 200 to 400 ° C. by the heater 26.
- Step S2 First precursor gas adsorption step: step S2
- the substrate to be processed W is sent to the first region R ⁇ b> 1 by the rotation of the mounting table 14.
- step S2 the first precursor gas is supplied to the first region R1.
- step S2 the first precursor gas is chemically adsorbed on the surface of the substrate to be processed W.
- dichlorosilane (DCS) is supplied to the first region at a flow rate of 30 sccm as the first precursor gas.
- step S3 Next, as the mounting table 14 rotates, the substrate to be processed W passes below the ejection port 20a.
- the first precursor gas excessively adsorbed on the substrate W to be processed is removed by the inert gas injected from the injection port 20a at this time.
- the inert gas is Ar gas and the flow rate is 540 sccm.
- step S4 the reactive gas is supplied to the second region R2, and the microwave is supplied as a plasma source.
- hydrogen gas ie, H 2 gas
- the microwave is supplied as a reactive gas to the second region R2 at a flow rate of 60 sccm, and a microwave having a frequency of 2.45 GHz and a power of 3 kW is generated. It is supplied to the second area.
- hydrogen gas plasma is generated in the second region R2.
- chlorine is extracted from the first precursor gas layer adsorbed on the substrate W to be processed by a reduction reaction by hydrogen ions in the plasma.
- the pressure in the second region R2 is preferably 1 Torr (133.3 Pa) or more.
- the pressure in the second region R2 is preferably 1 Torr (133.3 Pa) to 50 Torr (6666 Pa), and more preferably 1 Torr (133.3 Pa) to 10 Torr (1333 Pa). Since a large amount of hydrogen ions is generated under such a high pressure, the reducing action of extracting chlorine from the first precursor gas layer is more suitably exhibited.
- Step S5 (Second precursor gas adsorption step: step S5)
- Steps S2 to S4 are repeated one or more times, and then Step S5 is performed.
- step S5 the substrate to be processed W reaches the first region R1 with the rotation of the mounting table 14, and at this time, the second precursor gas is supplied to the first region R1.
- the two precursor gases are chemically adsorbed on the surface of the substrate W to be processed.
- the second precursor gas is AsClH 2 gas and is supplied to the first region R1 at a flow rate of 30 sccm.
- step S6 Next, as the mounting table 14 rotates, the substrate to be processed W passes below the ejection port 20a.
- the second precursor gas excessively adsorbed on the substrate W to be processed is removed by the inert gas ejected from the ejection port 20a.
- the inert gas is Ar gas and the flow rate is 540 sccm.
- step S7 plasma processing is performed on the substrate to be processed W in the same manner as in step S4.
- hydrogen gas ie, H 2 gas
- a microwave having a frequency of 2.45 GHz and a power of 3 kW is generated. It is supplied to the second area.
- hydrogen gas plasma is generated in the second region R2.
- chlorine is extracted from the layer of the second precursor gas adsorbed on the substrate to be processed W by a reduction reaction by hydrogen ions in the plasma.
- a layer of dopant material is formed on the substrate W to be processed.
- an As layer is formed.
- the pressure in the second region R2 in the step S7 is also preferably 1 Torr or more, as in the step S4.
- step S8 it is determined whether or not to end a series of steps S2 to S7.
- the number of repetitions of steps S1 to S7 is set in advance, and when the number of repetitions of steps S1 to S7 exceeds a predetermined number, the method proceeds to step S9.
- step S9 the substrate W to be processed is transferred to the process module PM2.
- a cap layer is formed on the surface of the substrate W to be processed in the process module PM2.
- the cap layer supplies BTBAS to the first region R1 and NH 3 gas in the second region R2 in the process module PM2, which is another film forming device having the same configuration as the film forming device 10. It is possible to form a film by generating the plasma.
- the substrate W to be processed is transferred from the process module PM2 to the process module PM3.
- an annealing process is performed on the substrate to be processed W.
- substrate W is activated.
- the substrate to be processed W is heated at a temperature of 1050 ° C. for about 1 second in an N 2 gas atmosphere. This heating is preferably performed, for example, for 0.1 to 10 seconds, and more preferably for 0.5 to 5 seconds.
- the film containing the dopant can be activated by such short-time annealing, and excessive diffusion of the dopant can be suppressed.
- the film forming method described above is a film forming method based on the ALD method, it is possible to form a film containing a dopant so as to follow a three-dimensional surface with high uniformity. Further, by adjusting the ratio between the number of executions of the step S2 for adsorbing the first precursor gas to the substrate W to be processed and the number of executions of the step S5 for adsorbing the second precursor gas to the substrate W to be processed, It is possible to adjust the concentration of the dopant therein.
- FIG. 15 is a flowchart showing a film forming method according to another embodiment.
- the mixed gas of the first precursor gas and the second precursor gas is supplied to the first region R ⁇ b> 1 in step S ⁇ b> 22, so that the mixing is performed on the substrate W to be processed. It differs from the film forming method shown in FIG. 14 in that gas is adsorbed.
- the dopant in the film to be formed on the substrate W to be processed is adjusted. The density can be adjusted.
- the film forming apparatus 10 described above is a semi-batch type film forming apparatus
- a film forming apparatus shown in FIG. 16 can be used as a film forming apparatus for forming a film containing a dopant.
- a film forming apparatus 10A shown in FIG. 16 is a single-wafer type film forming apparatus having a processing head for supplying a precursor gas.
- the film forming apparatus 10A includes a processing container 12A, a mounting table 14A that holds the substrate to be processed W in the processing container 12A, and a plasma generation unit 22A that generates a reactive gas plasma in the processing container 12A. ing.
- the plasma generation unit 22A includes a microwave generator 202 that generates a microwave for plasma excitation, and a radial line slot antenna 204 for introducing the microwave into the processing vessel 12A.
- the microwave generator 202 is connected via a waveguide 206 to a mode converter 208 that converts a microwave mode.
- the mode converter 208 is connected to the radial line slot antenna 204 via a coaxial waveguide 210 having an inner waveguide 210a and an outer waveguide 210b.
- the microwave generated by the microwave generator 202 is mode-converted by the mode converter 208 and reaches the radial line slot antenna 204.
- the frequency of the microwave generated by the microwave generator 202 is, for example, 2.45 GHz.
- the radial line slot antenna 204 includes a dielectric window 212 that closes the opening 120a formed in the processing container 12A, a slot plate 214 provided immediately above the dielectric window 34, a cooling jacket 216 provided above the slot plate 214, And a dielectric plate 218 disposed between the slot plate 214 and the cooling jacket 216.
- the slot plate 214 has a substantially disc shape.
- the slot plate 214 is provided with a plurality of slot pairs including two slot holes extending in a direction orthogonal to or intersecting with each other so as to be arranged in the radial direction and the circumferential direction of the slot plate 214.
- the dielectric window 212 is provided so as to face the substrate W to be processed.
- An inner waveguide 210 a is connected to the center of the slot plate 214, and an outer waveguide 210 b is connected to the cooling jacket 216.
- the cooling jacket 216 also functions as a waveguide. Thereby, the microwave propagating between the inner waveguide 210 a and the outer waveguide 210 b is transmitted through the dielectric plate 218 and the dielectric window 212 while reflecting between the slot plate 214 and the cooling jacket 216. Then, it reaches into the processing container 12A.
- a reaction gas supply port 120b is formed on the side wall of the processing vessel 12A.
- a reaction gas supply source 220 is connected to the supply port 120b.
- hydrogen gas can be used as described above. In the film forming apparatus 10A, this reactive gas is irradiated with microwaves, thereby generating reactive gas plasma.
- the exhaust port 120c for exhausting the gas in the processing container 12A is formed at the bottom of the processing container 12A.
- a vacuum pump 224 is connected to the exhaust port 120 c via a pressure regulator 222.
- a temperature controller 226 for adjusting the temperature of the mounting table 14A is connected to the mounting table 14A.
- the film forming apparatus 10A further includes a head part 240 in which an injection port 240a for injecting the first precursor gas, the second precursor gas, and the purge gas is formed.
- the head part 240 is connected to the driving device 244 via the support part 242.
- the driving device 244 is disposed outside the processing container 12A.
- the drive unit 244 allows the head unit 240 to move between a position facing the mounting table 14A and a retreat space 120d defined in the processing container 12A. When the head unit 240 is located in the retreat space 120d, the shutter 246 moves to isolate the retreat space 120d.
- the support part 242 defines a gas supply path for supplying gas to the injection port 240a.
- the gas supply path of the support part 242 includes a first precursor gas supply source 246, a second A precursor gas supply source 248 and a purge gas supply source 250 are connected. These supply sources 246, 248, and 250 are all gas supply sources capable of controlling the flow rate. Therefore, the first precursor gas, the second precursor gas, and the purge gas can be selectively injected from the head portion 240 onto the substrate W to be processed.
- the film forming apparatus 10A includes a control unit 256.
- the control unit 256 is connected to the microwave generator 202, the vacuum pump 224, the temperature controller 226, the driving device 244, and the supply sources 220, 246, 248, 250. Thereby, the control unit 256 outputs the microwave output, the pressure in the processing container 12A, the temperature of the mounting table 14A, the movement of the head unit 240, and the reaction gas, the first precursor gas, the second precursor gas, The gas flow rate and supply timing of the purge gas can be controlled respectively.
- the head unit 240 of the film forming apparatus 10A can define a small space supplied with the first precursor gas, the second precursor gas, and the purge gas between the mounting table 14A. Moreover, plasma of a reactive gas can be always generated in the processing container 12A. According to such a film forming apparatus, a space for supplying the precursor gas can be reduced, and plasma can be generated in the processing container 12A at all times, so that high throughput can be realized. Can do.
- a single-wafer type film forming apparatus that does not have the head unit 240 may be used.
- the gas supplied into the processing container is switched in the order of the first precursor gas, the purge gas, the reactive gas, the second precursor gas, the purge gas, the reactive gas, and the purge gas.
- a film containing the above-described dopant can be formed.
- the process module PM3 described above heats the substrate to be processed W and performs annealing.
- the process module for activating the film containing the dopant the substrate W to be processed is irradiated with microwaves.
- a process module may be used.
- a precursor gas such as silane, disilane, methylsilane, dimethylsilane, chlorosilane (SiH 3 Cl), or trichlorosilane (SiHCl 3 ) may be used instead of DCS.
- a mixed gas of B 2 H 6 and He, BF 3 , AsH 3 , AsH 4 , or PH 3 gas may be used.
- the reaction gas may contain oxygen gas in addition to hydrogen gas.
- the above-described embodiment mainly relates to the formation of a film containing silicon and a dopant.
- the film instead of silicon, other semiconductor materials or compound semiconductors such as III-V group compound semiconductors are used. It may contain material.
- a doping treatment method is a method of doping a substrate to be treated with a desired dopant.
- a first semiconductor material is contained in a chamber (processing vessel) in which a substrate to be treated is disposed. And (b) supplying a second precursor gas of a dopant material into a processing vessel and adsorbing it to the substrate to be processed; (c) And a step of performing plasma treatment in an atmospheric gas so as to dope the atomic adsorption layer adsorbed on the substrate to be treated in the treatment container.
- the plasma may be excited by microwaves.
- a first precursor gas and a second precursor gas are adsorbed on a substrate to be treated by an ALD (Atomic Layer Deposition) method, and then an atomic adsorption layer of a dopant adsorbed on the substrate to be treated is plasma-treated.
- ALD Atomic Layer Deposition
- an atomic adsorption layer of a dopant adsorbed on the substrate to be treated is plasma-treated.
- Doping by treatment it is possible to form a film containing a dopant uniformly and conformally on a surface having a three-dimensional structure, that is, a plurality of surfaces having different directions. Conformal indicates a state where the surface having a three-dimensional structure is uniformly doped without uneven concentration.
- SYMBOLS 10 ... Film-forming apparatus, 12 ... Processing container, 14 ... Mounting stand, 16 ... Gas supply part (supply part of 1st and 2nd precursor gas), 20 ... Gas supply part (supply part of purge gas), 22 ... Plasma generating unit, 60 ... control unit, 100 ... film forming system, PM1 ... process module (film forming apparatus), PM2 ... process module (another film forming apparatus), PM3 ... process module (annealing apparatus), W ... processed Substrate.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Electromagnetism (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
成膜装置10では、まず、載置台14の回転により、被処理基体Wが第1の領域R1に送られる。工程S2の実施時には、第1の領域R1には、第1の前駆体ガスが供給されている。したがって、工程S2では、第1の前駆体ガスが被処理基体Wの表面に化学吸着する。一実施形態においては、第1の前駆体ガスとして、ジクロロシラン(DCS)が、流量30sccmで第1の領域に供給される。
次いで、載置台14の回転に伴い、被処理基体Wが噴射口20aの下方を通過する。工程S3では、このとき、噴射口20aから噴射される不活性ガスにより、被処理基体Wに過剰に吸着した第1の前駆体ガスが除去される。一実施形態においては、不活性ガスはArガスであり、その流量は540sccmである。
次いで、載置台14の回転に伴い、被処理基体Wは第2の領域R2に至る。工程S4の実施時には、第2の領域R2に、反応ガスが供給されており、また、プラズマ源としてマイクロ波が供給されている。一実施形態においては、反応ガスとして水素ガス、即ちH2ガスが60sccmの流量で第2の領域R2に供給されており、また、2.45GHzの周波数を有し3kWのパワーを有するマイクロ波が第2の領域に供給されている。これにより、第2の領域R2では水素ガスのプラズマが生成されている。第2の領域R2においては、プラズマ中の水素イオンによる還元反応により、被処理基体Wに吸着されている第1の前駆体ガスの層から塩素が引き出される。これにより、被処理基体Wにはシリコン原子の層が形成される。なお、第2の領域R2の圧力は、1Torr(133.3Pa)以上であることが好ましい。例えば、第2の領域R2の圧力は、1Torr(133.3Pa)~50Torr(6666Pa)であることが好ましく、1Torr(133.3Pa)~10Torr(1333Pa)であることがより好ましい。かかる高圧下では水素イオンが多量に発生するので、第1の前駆体ガスの層から塩素を引き抜く還元作用がより好適に発揮される。
本方法では、工程S2~S4が1回以上繰り返された後、工程S5が実施される。工程S5では、載置台14の回転に伴い、被処理基体Wが第1の領域R1に至り、このとき、第1の領域R1には、第2の前駆体ガスが供給されており、当該第2の前駆体ガスが被処理基体Wの表面に化学吸着する。一実施形態では、第2の前駆体ガスは、AsClH2ガスであり、流量30sccmで第1の領域R1に供給される。
次いで、載置台14の回転に伴い、被処理基体Wが噴射口20aの下方を通過する。工程S6では、噴射口20aから噴射される不活性ガスにより、被処理基体Wに過剰に吸着した第2の前駆体ガスが除去される。一実施形態においては、不活性ガスはArガスであり、その流量は540sccmである。
次いで、載置台14の回転に伴い、被処理基体Wは第2の領域R2に至る。工程S7では、工程S4と同様に、被処理基体Wに対するプラズマ処理が行われる。一実施形態においては、反応ガスとして水素ガス、即ちH2ガスが60sccmの流量で第2の領域R2に供給されており、また、2.45GHzの周波数を有し3kWのパワーを有するマイクロ波が第2の領域に供給されている。これにより、第2の領域R2では水素ガスのプラズマが生成されている。第2の領域R2においては、プラズマ中の水素イオンによる還元反応により、被処理基体Wに吸着されている第2の前駆体ガスの層から塩素が引き出される。これにより、被処理基体Wにはドーパント材料の層が形成される。本実施形態では、Asの層が形成される。なお、工程S7における第2の領域R2の圧力も、工程S4と同様に、1Torr以上であることが好ましい。
Claims (20)
- その内部に被処理基体が配置された処理容器内に半導体材料の第1の前駆体ガスを供給する工程であり、該第1の前駆体ガスを前記被処理基体に吸着させる、該工程と、
前記処理容器内にドーパント材料の第2の前駆体ガスを供給する工程であり、該第2の前駆体ガスを前記被処理基体に吸着させる、該工程と、
前記処理容器内において反応ガスのプラズマを生成する工程であり、前記被処理基体に吸着した層を改質するようプラズマ処理を行う、該工程と、
を含む成膜方法。 - 前記第1の前駆体ガスを供給する工程と前記第2の前駆体ガスを供給する工程が別個に行われる、請求項1に記載の成膜方法。
- 前記プラズマを生成する工程は、第1のプラズマ処理を行う工程と第2のプラズマ処理を行う工程を含み、
前記第1のプラズマ処理を行う工程では、前記第1の前駆体ガスを供給する工程により前記被処理基体に吸着した層に対して、前記反応ガスのプラズマによるプラズマ処理が行われ、
前記第2のプラズマ処理を行う工程では、前記第2の前駆体ガスを供給する工程により前記被処理基体に吸着した層に対してプラズマ処理が行われる、
請求項2に記載の成膜方法。 - 前記第1の前駆体ガス及び前記第2の前駆体ガスはそれぞれ、水素原子及び塩素原子のうち一以上を更に含み、
前記第1のプラズマ処理を行う工程及び前記第2のプラズマ処理を行う工程において、前記反応ガスである水素ガスのプラズマが励起される、
請求項3に記載の成膜方法。 - 前記第1の前駆体ガスを供給する工程と前記第2の前駆体ガスを供給する工程とを同時に実施することにより、前記被処理基体に前記第1の前駆体ガスと前記第2の前駆体ガスの混合ガスを吸着させる、請求項1に記載の成膜方法。
- 前記第1の前駆体ガス及び前記第2の前駆体ガスはそれぞれ、水素原子及び塩素原子のうち一以上を更に含み、
前記プラズマ処理を行う工程では、前記反応ガスである水素ガスのプラズマが励起される、
請求項5に記載の成膜方法。 - 前記プラズマ処理を行う工程では、マイクロ波によってプラズマが励起される、請求項1~6の何れか一項に記載の成膜方法。
- 前記プラズマ処理を行う工程では、前記処理容器内の圧力が133.3Pa~6666Paの範囲内の圧力に設定される、請求項7に記載の成膜方法。
- 前記第1の前駆体ガスを吸着させる工程、前記第2の前駆体ガスを吸着させる工程、及び、前記プラズマを生成する工程を含む一連の工程を一回以上繰り返した後に、前記被処理基体をアニールする工程を更に含む、請求項1~8の何れか一項に記載の成膜方法。
- 前記被処理基体をアニールする工程は、0.1~10秒間行われる請求項9に記載の成膜方法。
- 前記被処理基体をアニールする工程の前に、前記被処理基体の上に形成された膜の表面にキャップ層を形成する工程を更に含む、請求項9又は10に記載の成膜方法。
- その内部に被処理基体が配置される処理容器と、
半導体材料の第1の前駆体ガス、及び、ドーパント材料の第2の前駆体ガスを前記被処理基体に吸着させるよう前記処理容器内に該第1の前駆体ガス及び該第2の前駆体ガスを供給する供給部と、
前記被処理基体に吸着した層をプラズマ処理により改質するよう前記処理容器内において反応ガスのプラズマを生成するプラズマ生成部と、
を備える成膜装置。 - 前記供給部及び前記プラズマ生成部を制御する制御部を更に備える、請求項12に記載の成膜装置。
- 前記制御部は、
前記処理容器内に前記第1の前駆体ガスを供給するよう前記供給部を制御し、
前記第1の前駆体ガスの供給により前記被処理基体に吸着した層に対してプラズマ処理を行うために前記反応ガスのプラズマを生成するよう前記プラズマ生成部を制御し、
前記処理容器内に前記第2の前駆体ガスを供給するよう前記供給部を制御し、
前記第2のガスの供給により前記被処理基体に吸着した層に対してプラズマ処理を行うために前記反応ガスのプラズマを生成するよう前記プラズマ生成部を制御する、
請求項13に記載の成膜装置。 - 前記供給部は、前記第1の前駆体ガスと前記第2の前駆体ガスの混合ガスを前記処理容器内に供給し、
前記制御部は、
前記処理容器内に前記混合ガスを供給するよう前記供給部を制御し、
前記混合ガスの供給により前記被処理基体に吸着した層に対してプラズマ処理を行うために前記反応ガスのプラズマを生成するよう前記プラズマ生成部を制御する、
請求項13又は14に記載の成膜装置。 - 前記第1のガス及び前記第2のガスはそれぞれ、水素原子及び塩素原子のうち一以上を更に含み、
前記プラズマ生成部は、前記反応ガスである水素ガスのプラズマを生成する、
請求項12~15の何れか一項に記載の成膜装置。 - 前記プラズマ生成部は、マイクロ波により前記反応ガスのプラズマを励起する、請求項12~16の何れか一項に記載の成膜装置。
- 前記成膜装置は、ALD成膜を利用したドーピングシステムの成膜装置である、請求項12~17の何れか一項に記載の成膜装置。
- 請求項12~18の何れか一項に記載の成膜装置と、
前記成膜装置によって処理された被処理基体を受け入れて、該被処理基体をアニールするアニール装置と、
を備える成膜システム。 - 前記成膜装置と真空搬送系を介して接続されており、前記成膜装置から被処理基体を受け入れて、該被処理基体の表面にキャップ層を形成する別の成膜装置を更に備え、
前記アニール装置は前記別の成膜装置から搬送された被処理基体をアニールするよう該別の成膜装置に接続されている、
請求項19に記載の成膜システム。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020147029650A KR20140147109A (ko) | 2012-04-23 | 2013-04-22 | 성막 방법, 성막 장치, 및 성막 시스템 |
JP2014512561A JP5926794B2 (ja) | 2012-04-23 | 2013-04-22 | 成膜方法、成膜装置、及び、成膜システム |
US14/395,690 US20150087140A1 (en) | 2012-04-23 | 2013-04-22 | Film forming method, film forming device, and film forming system |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012097624 | 2012-04-23 | ||
JP2012-097624 | 2012-04-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013161768A1 true WO2013161768A1 (ja) | 2013-10-31 |
Family
ID=49483081
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/061803 WO2013161768A1 (ja) | 2012-04-23 | 2013-04-22 | 成膜方法、成膜装置、及び、成膜システム |
Country Status (5)
Country | Link |
---|---|
US (1) | US20150087140A1 (ja) |
JP (1) | JP5926794B2 (ja) |
KR (1) | KR20140147109A (ja) |
TW (1) | TW201405634A (ja) |
WO (1) | WO2013161768A1 (ja) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014165402A (ja) * | 2013-02-26 | 2014-09-08 | Tokyo Electron Ltd | 窒化膜を形成する方法 |
JP2015199998A (ja) * | 2014-04-09 | 2015-11-12 | 東京エレクトロン株式会社 | 基板処理装置および基板処理方法 |
JP2017503359A (ja) * | 2014-01-13 | 2017-01-26 | アプライド マテリアルズ インコーポレイテッドApplied Materials,Incorporated | 空間的原子層堆積法による、自己整合ダブルパターニング |
JP2017528916A (ja) * | 2014-09-10 | 2017-09-28 | アプライド マテリアルズ インコーポレイテッドApplied Materials,Incorporated | 空間的原子層堆積におけるガス分離制御 |
JP2018026524A (ja) * | 2016-08-08 | 2018-02-15 | 東京エレクトロン株式会社 | シリコン窒化膜の成膜方法および成膜装置 |
JPWO2018012049A1 (ja) * | 2016-07-14 | 2019-02-14 | 株式会社Kokusai Electric | 半導体装置の製造方法、基板処理装置及びプログラム |
JP2021034428A (ja) * | 2019-08-19 | 2021-03-01 | 東京エレクトロン株式会社 | 成膜方法及び成膜装置 |
JP2022501826A (ja) * | 2018-09-29 | 2022-01-06 | アプライド マテリアルズ インコーポレイテッドApplied Materials, Incorporated | 正確な温度及び流量制御を備えたマルチステーションチャンバリッド |
JP2022543749A (ja) * | 2019-08-01 | 2022-10-14 | アプライド マテリアルズ インコーポレイテッド | トランジスタのヒ素拡散プロファイルエンジニアリング |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160002784A1 (en) * | 2014-07-07 | 2016-01-07 | Varian Semiconductor Equipment Associates, Inc. | Method and apparatus for depositing a monolayer on a three dimensional structure |
JP6479550B2 (ja) * | 2015-04-22 | 2019-03-06 | 東京エレクトロン株式会社 | プラズマ処理装置 |
JP6479560B2 (ja) * | 2015-05-01 | 2019-03-06 | 東京エレクトロン株式会社 | 成膜装置 |
US10861667B2 (en) * | 2017-06-27 | 2020-12-08 | Peter F. Vandermeulen | Methods and systems for plasma deposition and treatment |
KR20190005741A (ko) * | 2017-07-07 | 2019-01-16 | 도쿄엘렉트론가부시키가이샤 | 반도체 장치의 제조 방법 및 금속 산화물 막의 형성 방법 |
US11462630B2 (en) | 2017-09-03 | 2022-10-04 | Applied Materials, Inc. | Conformal halogen doping in 3D structures using conformal dopant film deposition |
KR101999771B1 (ko) | 2018-07-20 | 2019-07-12 | 주식회사 대양에스티 | 식기세척기용 식기투입기 |
CN110416071A (zh) * | 2019-08-01 | 2019-11-05 | 江苏微导纳米装备科技有限公司 | 一种晶体硅太阳能电池的硅基薄膜镀膜方法 |
KR102290543B1 (ko) | 2019-08-02 | 2021-08-18 | 주식회사 대양에스티 | 식판 담금형 애벌세척기 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08255759A (ja) * | 1995-03-17 | 1996-10-01 | Canon Inc | 多結晶Si薄膜の堆積法 |
JP2006229070A (ja) * | 2005-02-18 | 2006-08-31 | Hitachi Kokusai Electric Inc | 半導体装置の製造方法 |
JP2010520638A (ja) * | 2007-03-06 | 2010-06-10 | ヴァリアン セミコンダクター イクイップメント アソシエイツ インコーポレイテッド | 原子層堆積の技術 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU8675798A (en) * | 1997-07-29 | 1999-02-22 | Silicon Genesis Corporation | Cluster tool method and apparatus using plasma immersion ion implantation |
KR100373853B1 (ko) * | 2000-08-11 | 2003-02-26 | 삼성전자주식회사 | 반도체소자의 선택적 에피택시얼 성장 방법 |
US7540920B2 (en) * | 2002-10-18 | 2009-06-02 | Applied Materials, Inc. | Silicon-containing layer deposition with silicon compounds |
US9121098B2 (en) * | 2003-02-04 | 2015-09-01 | Asm International N.V. | NanoLayer Deposition process for composite films |
WO2004113585A2 (en) * | 2003-06-18 | 2004-12-29 | Applied Materials, Inc. | Atomic layer deposition of barrier materials |
US20070087581A1 (en) * | 2005-09-09 | 2007-04-19 | Varian Semiconductor Equipment Associates, Inc. | Technique for atomic layer deposition |
US8637411B2 (en) * | 2010-04-15 | 2014-01-28 | Novellus Systems, Inc. | Plasma activated conformal dielectric film deposition |
-
2013
- 2013-04-22 JP JP2014512561A patent/JP5926794B2/ja active Active
- 2013-04-22 US US14/395,690 patent/US20150087140A1/en not_active Abandoned
- 2013-04-22 WO PCT/JP2013/061803 patent/WO2013161768A1/ja active Application Filing
- 2013-04-22 KR KR1020147029650A patent/KR20140147109A/ko not_active Application Discontinuation
- 2013-04-23 TW TW102114365A patent/TW201405634A/zh unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08255759A (ja) * | 1995-03-17 | 1996-10-01 | Canon Inc | 多結晶Si薄膜の堆積法 |
JP2006229070A (ja) * | 2005-02-18 | 2006-08-31 | Hitachi Kokusai Electric Inc | 半導体装置の製造方法 |
JP2010520638A (ja) * | 2007-03-06 | 2010-06-10 | ヴァリアン セミコンダクター イクイップメント アソシエイツ インコーポレイテッド | 原子層堆積の技術 |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014165402A (ja) * | 2013-02-26 | 2014-09-08 | Tokyo Electron Ltd | 窒化膜を形成する方法 |
JP2017503359A (ja) * | 2014-01-13 | 2017-01-26 | アプライド マテリアルズ インコーポレイテッドApplied Materials,Incorporated | 空間的原子層堆積法による、自己整合ダブルパターニング |
JP2015199998A (ja) * | 2014-04-09 | 2015-11-12 | 東京エレクトロン株式会社 | 基板処理装置および基板処理方法 |
KR101781683B1 (ko) | 2014-04-09 | 2017-09-25 | 도쿄엘렉트론가부시키가이샤 | 기판 처리 장치 및 기판 처리 방법 |
US11230763B2 (en) | 2014-09-10 | 2022-01-25 | Applied Materials, Inc. | Gas separation control in spatial atomic layer deposition |
JP2017528916A (ja) * | 2014-09-10 | 2017-09-28 | アプライド マテリアルズ インコーポレイテッドApplied Materials,Incorporated | 空間的原子層堆積におけるガス分離制御 |
US11821083B2 (en) | 2014-09-10 | 2023-11-21 | Applied Materials, Inc. | Gas separation control in spatial atomic layer deposition |
JPWO2018012049A1 (ja) * | 2016-07-14 | 2019-02-14 | 株式会社Kokusai Electric | 半導体装置の製造方法、基板処理装置及びプログラム |
JP2018026524A (ja) * | 2016-08-08 | 2018-02-15 | 東京エレクトロン株式会社 | シリコン窒化膜の成膜方法および成膜装置 |
JP2022501826A (ja) * | 2018-09-29 | 2022-01-06 | アプライド マテリアルズ インコーポレイテッドApplied Materials, Incorporated | 正確な温度及び流量制御を備えたマルチステーションチャンバリッド |
JP7121447B2 (ja) | 2018-09-29 | 2022-08-18 | アプライド マテリアルズ インコーポレイテッド | 正確な温度及び流量制御を備えたマルチステーションチャンバリッド |
JP2022176935A (ja) * | 2018-09-29 | 2022-11-30 | アプライド マテリアルズ インコーポレイテッド | 正確な温度及び流量制御を備えたマルチステーションチャンバリッド |
JP7441900B2 (ja) | 2018-09-29 | 2024-03-01 | アプライド マテリアルズ インコーポレイテッド | 正確な温度及び流量制御を備えたマルチステーションチャンバリッド |
JP2022543749A (ja) * | 2019-08-01 | 2022-10-14 | アプライド マテリアルズ インコーポレイテッド | トランジスタのヒ素拡散プロファイルエンジニアリング |
JP7335418B2 (ja) | 2019-08-01 | 2023-08-29 | アプライド マテリアルズ インコーポレイテッド | トランジスタのヒ素拡散プロファイルエンジニアリング |
JP7200880B2 (ja) | 2019-08-19 | 2023-01-10 | 東京エレクトロン株式会社 | 成膜方法及び成膜装置 |
JP2021034428A (ja) * | 2019-08-19 | 2021-03-01 | 東京エレクトロン株式会社 | 成膜方法及び成膜装置 |
Also Published As
Publication number | Publication date |
---|---|
TW201405634A (zh) | 2014-02-01 |
KR20140147109A (ko) | 2014-12-29 |
JP5926794B2 (ja) | 2016-05-25 |
JPWO2013161768A1 (ja) | 2015-12-24 |
US20150087140A1 (en) | 2015-03-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5926794B2 (ja) | 成膜方法、成膜装置、及び、成膜システム | |
JP7048575B2 (ja) | ギャップを充填する方法及び装置 | |
KR101660615B1 (ko) | 성막 장치 | |
KR101553554B1 (ko) | 실리콘 질화물 전하 트랩 층을 갖는 비-휘발성 메모리 | |
JP5839606B2 (ja) | 窒化膜を形成する方法 | |
US10573512B2 (en) | Film forming method | |
KR101657341B1 (ko) | 성막 방법 | |
JP2019511118A (ja) | スペーサ用の窒化ケイ素膜の選択的堆積 | |
SG192375A1 (en) | Method for depositing a chlorine-free conformal sin film | |
US20080173908A1 (en) | Multilayer silicon nitride deposition for a semiconductor device | |
KR20100027062A (ko) | 활성화 가스 인젝터, 성막 장치 및 성막 방법 | |
KR20170092462A (ko) | 성막 방법 | |
WO2006055459A2 (en) | Tensile and compressive stressed materials for semiconductors | |
WO2005093800A1 (ja) | 不純物導入方法、不純物導入装置およびこの方法を用いて形成された半導体装置 | |
US9245793B2 (en) | Plasma treatment of low-K surface to improve barrier deposition | |
US11131023B2 (en) | Film deposition apparatus and film deposition method | |
TWI756705B (zh) | 添加氬至遠端電漿氧化 | |
US11823901B2 (en) | System and method for radical and thermal processing of substrates | |
TWI702304B (zh) | 矽氮化膜之成膜方法及成膜裝置 | |
JP2009164519A (ja) | 低温ポリシリコン用保護膜の成膜方法、低温ポリシリコン用保護膜の成膜装置および低温ポリシリコンtft | |
US7700499B2 (en) | Multilayer silicon nitride deposition for a semiconductor device | |
US20150140836A1 (en) | Methods to Control SiO2 Etching During Fluorine Doping of Si/SiO2 Interface | |
KR100940824B1 (ko) | 실리콘 화합물의 형성방법 | |
US20110210401A1 (en) | Multilayer silicon nitride deposition for a semiconductor device | |
TW200841385A (en) | Film forming apparatus and method of forming film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13781071 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014512561 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14395690 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20147029650 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13781071 Country of ref document: EP Kind code of ref document: A1 |