WO2007139142A1 - プラズマcvd方法、窒化珪素膜の形成方法、半導体装置の製造方法およびプラズマcvd装置 - Google Patents
プラズマcvd方法、窒化珪素膜の形成方法、半導体装置の製造方法およびプラズマcvd装置 Download PDFInfo
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- WO2007139142A1 WO2007139142A1 PCT/JP2007/060976 JP2007060976W WO2007139142A1 WO 2007139142 A1 WO2007139142 A1 WO 2007139142A1 JP 2007060976 W JP2007060976 W JP 2007060976W WO 2007139142 A1 WO2007139142 A1 WO 2007139142A1
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- Prior art keywords
- silicon nitride
- nitride film
- plasma
- gas
- processing chamber
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 172
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 238000000034 method Methods 0.000 title claims abstract description 68
- 238000005268 plasma chemical vapour deposition Methods 0.000 title claims description 65
- 239000004065 semiconductor Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000007789 gas Substances 0.000 claims abstract description 187
- 238000012545 processing Methods 0.000 claims abstract description 171
- 239000000758 substrate Substances 0.000 claims abstract description 33
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000151 deposition Methods 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- 230000007246 mechanism Effects 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 239000010408 film Substances 0.000 description 202
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 230000005855 radiation Effects 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000000137 annealing Methods 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- 229920005591 polysilicon Polymers 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 230000000644 propagated effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- -1 nitrogen-containing compound Chemical class 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910020776 SixNy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000003187 abdominal effect Effects 0.000 description 1
- VOSJXMPCFODQAR-UHFFFAOYSA-N ac1l3fa4 Chemical compound [SiH3]N([SiH3])[SiH3] VOSJXMPCFODQAR-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
-
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02211—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound being a silane, e.g. disilane, methylsilane or chlorosilane
-
- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/318—Inorganic layers composed of nitrides
- H01L21/3185—Inorganic layers composed of nitrides of siliconnitrides
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- 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
- H01L29/401—Multistep manufacturing processes
- H01L29/4011—Multistep manufacturing processes for data storage electrodes
- H01L29/40114—Multistep manufacturing processes for data storage electrodes the electrodes comprising a conductor-insulator-conductor-insulator-semiconductor structure
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- 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
- H01L29/7842—Field effect transistors with field effect produced by an insulated gate means for exerting mechanical stress on the crystal lattice of the channel region, e.g. using a flexible substrate
- H01L29/7843—Field effect transistors with field effect produced by an insulated gate means for exerting mechanical stress on the crystal lattice of the channel region, e.g. using a flexible substrate the means being an applied insulating layer
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10B—ELECTRONIC MEMORY DEVICES
- H10B69/00—Erasable-and-programmable ROM [EPROM] devices not provided for in groups H10B41/00 - H10B63/00, e.g. ultraviolet erasable-and-programmable ROM [UVEPROM] devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
Definitions
- Plasma CVD method silicon nitride film formation method, semiconductor device manufacturing method, and plasma CVD device
- the present invention relates to a CVD (Chemical Vapor Deposition) method using plasma, a method of forming a silicon nitride film and a method of manufacturing a semiconductor device using the method, and a plasma CVD device used in these processes.
- CVD Chemical Vapor Deposition
- a silicon nitride film is used as an insulating film or a protective film in various semiconductor devices.
- Such a silicon nitride film for example, contains silicon such as silane (SiH) as a source gas.
- An object of the present invention is to provide a plasma CVD method capable of imparting high stress to a silicon nitride film to be formed and having less plasma damage.
- Another object of the present invention is to provide a method of forming a silicon nitride film that can introduce a desired stress using such plasma CVD.
- Still another object of the present invention is to provide a method of manufacturing a semiconductor device using such a silicon nitride film.
- Still another object of the present invention is to provide a plasma CVD apparatus capable of performing the plasma CVD method as described above.
- a processing chamber capable of being evacuated, a mounting table for mounting a processing object in the processing chamber, a microwave generation source for generating microwaves, and a plurality of A planar antenna for introducing a microwave generated by the microwave generation source into the processing chamber through the slot; a gas supply mechanism for supplying a film forming source gas into the processing chamber; Preparing a plasma processing apparatus including a high-frequency power source for supplying high-frequency power to the table, placing a substrate to be processed on the table, and introducing a nitrogen-containing gas and a silicon-containing gas into the processing chamber Then, these gases are turned into plasma by the microwave, and when the silicon nitride film is deposited on the surface of the substrate to be processed by the plasma, and the silicon nitride film is deposited, the high frequency electric power is applied to the mounting table. And a supplying a plasma CVD method is provided.
- a processing chamber capable of being evacuated, a mounting table on which a target object is mounted in the processing chamber, a microwave generation source for generating microwaves, and a plurality of A planar antenna for introducing a microwave generated by the microwave generation source into the processing chamber through the slot; a gas supply mechanism for supplying a film forming source gas into the processing chamber;
- a plasma processing apparatus having a high frequency power source for supplying high frequency power to a table Preparing a substrate to be processed on the mounting table, introducing a nitrogen-containing gas and a silicon-containing gas into the processing chamber, converting the gas into plasma by the microwave, and processing the plasma with the plasma
- a method for forming a silicon nitride film comprising: depositing a silicon nitride film on a surface of a substrate; and supplying high frequency power to the mounting table when depositing the silicon nitride film.
- the power density of the high-frequency power is 0.
- the frequency can be selected from 400 kHz to 27 MHz.
- a silicon nitride film having a compressive stress of lOOOMPa or more can be formed. In this case, it is preferable to deposit the silicon nitride film at a processing pressure of 0.1 lPa or more and 53 Pa or less. Furthermore, a silicon nitride film having a compressive stress of 2000 MPa or more can be formed. In this case, it is preferable to deposit the silicon nitride film at a processing pressure of 0.1 to 40 Pa. Furthermore, a silicon nitride film having a compressive stress of 3000 MPa or more can be formed.
- the silicon nitride film it is preferable to deposit the silicon nitride film at a processing pressure of 5 Pa or more and 25 Pa or less. It is preferable that the power density of 0. 016 ⁇ 0. 127 WZcm 2. Furthermore, a silicon nitride film having a compressive stress of 3500 MPa or more can be formed. In this case, it is preferable to deposit the silicon nitride film at a processing pressure of 7 Pa or more and 16 Pa or less. The power density is preferably 0.032 to 0.095 WZcm 2 .
- ammonia gas or nitrogen gas can be used as the nitrogen-containing gas.
- disilane (Si H) can be used as the silicon-containing gas.
- the processing temperature for depositing the silicon nitride film can be 300 ° C. to 800 ° C.
- a gate electrode is formed on a main surface of a semiconductor substrate via an insulating film, and a source and a drain are formed in main surface regions on both sides thereof.
- the silicon nitride film comprises a process chamber capable of being evacuated to the vacuum,
- a mounting table for mounting an object to be processed in a processing chamber, a microwave generation source for generating microwaves, and a plurality of slots, and the microwaves generated in the microwave generation source through the slots Planar antenna to be introduced indoors and front
- Preparing a plasma processing apparatus having a gas supply mechanism for supplying a film forming raw material gas into the processing chamber; placing a substrate to be processed on the mounting table; and containing a nitrogen-containing gas and silicon in the processing chamber.
- a method for manufacturing a semiconductor device is provided, which is formed by a method including supplying high-frequency power.
- a processing chamber that operates on a computer and can be evacuated, a mounting table on which an object to be processed is mounted in the processing chamber, and a microwave that generates microwaves A generation source, a planar antenna that has a plurality of slots and introduces microwaves generated by the microwave generation source into the processing chamber through the slots, and a gas that supplies a film forming raw material gas into the processing chamber
- a storage medium storing a program for controlling a plasma processing apparatus having a supply mechanism and a high-frequency power source for supplying high-frequency power to the mounting table, wherein the program is processed on the mounting table at the time of execution.
- a processing chamber capable of being evacuated, a mounting table for mounting a processing object in the processing chamber, a microwave generation source for generating microwaves, and a plurality of A planar antenna that has a slot and introduces the microwave generated by the microwave generation source into the processing chamber through the slot; a gas supply mechanism that supplies a film forming source gas into the processing chamber; A high-frequency power source for supplying high-frequency power to the mounting table; placing the substrate to be processed on the mounting table; introducing a nitrogen-containing gas and a silicon-containing gas into the processing chamber; And a plasma CVD method comprising: depositing a silicon nitride film on the surface of the substrate to be processed by the plasma; and supplying high-frequency power to the mounting table when the silicon nitride film is being deposited.
- a plasma processing apparatus provided with a control unit that controls so as to be performed.
- a processing chamber capable of vacuum evacuation for processing a substrate to be processed using plasma
- a mounting table for mounting the substrate to be processed in the processing chamber
- a planar antenna having a plurality of slots for introducing microwaves into the processing chamber
- a gas supply mechanism for supplying a film forming raw material gas into the processing chamber
- a high-frequency power source for supplying high-frequency power to the mounting table
- a plasma CVD apparatus is provided.
- a processing chamber capable of being evacuated, a mounting table for mounting the object to be processed in the processing chamber, a microwave generation source for generating microwaves, and a plurality of slots.
- a planar antenna that introduces microwaves generated by the microwave generation source into the processing chamber through the slot, a gas supply mechanism that supplies a film forming source gas into the processing chamber, and high-frequency power to the mounting table
- a plasma processing apparatus equipped with a high-frequency power supply to supply high-frequency power to the mounting table and depositing a silicon nitride film
- a high compression stress for example, lOOOMPa or higher, preferably 2000 MPa or higher, more preferably 3000 MPa
- a silicon nitride film having a compressive stress of 3500 MPa or more can be desirably formed. This effect can also be obtained regardless of the type of film forming gas.
- a plasma processing apparatus that generates a plasma by introducing a microwave into a processing chamber using a planar antenna having a plurality of slots can perform plasma processing at a low electron temperature and high density. Plasma damage in CVD can be reduced as much as possible. Therefore, by using the plasma processing apparatus, the range of selection of plasma CVD conditions such as the type of nitrogen-containing gas and processing pressure can be widened, and the controllability of stress on the silicon nitride film can be enhanced.
- the plasma CVD method of the present invention is a method capable of applying high compressive stress to the silicon nitride film and suppressing plasma damage. Therefore, the silicon nitride film having stress in the manufacturing process of various semiconductor devices. Can be advantageously used in forming a film.
- FIG. 1 is a schematic sectional view showing an example of a plasma processing apparatus suitable for carrying out the method of the present invention.
- FIG. 2 is a plan view showing a planar antenna member of the plasma processing apparatus of FIG.
- FIG. 3 A diagram showing typical current-voltage characteristics when a Langmuir probe is inserted into plasma and the applied voltage is swept. (4) Current-voltage characteristics when the bias power is changed.
- FIG. 5 is a graph showing the relationship between the noise power density and the electron temperature of plasma.
- FIG. 6 A diagram schematically showing a cross-sectional structure of a MOS transistor using a stressed silicon nitride film as a coating film.
- FIG. 7A is a process cross-sectional view illustrating a process of the method for manufacturing a semiconductor device to which the plasma CVD method according to an embodiment of the present invention is applied, and shows a state before the formation of the silicon nitride film.
- FIG. 7B is a process cross-sectional view illustrating a process of the method for manufacturing a semiconductor device to which the plasma CVD method according to one embodiment of the present invention is applied, and shows a state where the plasma CVD process is performed.
- FIG. 7C is a process cross-sectional view illustrating a process of the method for manufacturing a semiconductor device to which the plasma CVD method according to one embodiment of the present invention is applied, and shows a state where the plasma CVD process is performed.
- FIG. 7C is a process cross-sectional view showing a process of a semiconductor device manufacturing method to which the plasma CVD method according to an embodiment of the present invention is applied, and shows a state after forming a silicon nitride film having stress due to plasma CVD Figure.
- FIG. 8 A diagram schematically showing a cross-sectional structure of a CMOS transistor using a stressed silicon nitride film as a coating film.
- FIG. 9 A diagram schematically showing a cross-sectional structure of a nonvolatile memory using a stressed silicon nitride film as a coating film.
- FIG. 11 is a graph showing the relationship between the stress of the silicon nitride film and the RF power condition in plasma CVD.
- the graph which shows the relationship with RF power condition according to processing pressure in ma CVD.
- the graph which shows the relationship with RF power condition according to processing pressure in Zuma CVD.
- FIG. 15 is a graph showing the relationship between the stress of a silicon nitride film and the number RF power condition in plasma CVD, comparing the case of frequency power 00 kHz and 13.56 MHz.
- FIG. 1 is a cross-sectional view schematically showing an example of a plasma processing apparatus that can be used for forming a silicon nitride film in the method of the present invention.
- the plasma processing apparatus 100 has a high density and high density by generating plasma by introducing microwaves into a processing chamber using a planar antenna having a plurality of slots, particularly an RLSA (Radial Line Slot Antenna). It is configured as an RLSA microwave plasma processing device that can generate microwave-excited plasma with a low electron temperature, and it has a plasma density of 1 X 10 1G to 5 X 10 12 Zcm 3 and is powerfully low at 0.7 to 2 eV. Processing with plasma at electron temperature is possible. Therefore, it can be suitably used for the purpose of forming a silicon nitride film by plasma CVD in the manufacturing process of various semiconductor devices.
- the plasma processing apparatus 100 has a substantially cylindrical chamber 11 that is airtight and grounded.
- the chamber 11 may have a rectangular tube shape.
- a circular opening 10 is formed in a substantially central portion of the bottom wall la of the chamber 11, and an exhaust chamber 11 that communicates with the opening 10 and protrudes downward is provided on the bottom wall la. Yes.
- the exhaust chamber 11 is connected to an exhaust device 24 via an exhaust pipe 23.
- a silicon wafer (hereinafter simply referred to as a "wafer") W which is a substrate to be processed, is provided in the chamber 1 in order to horizontally support the W, and a mounting table 2 made of ceramics such as A1N having high thermal conductivity is provided. It has been.
- the mounting table 2 is supported by a support member 3 having a ceramic force such as a cylindrical A1N extending upward in the center of the bottom of the exhaust chamber 11.
- the mounting table 2 is provided with a cover ring 4 for covering the outer edge and guiding the wafer W.
- This cover ring 4 is made of, for example, quartz, A1N, Al O
- a member made of SiN or other material A member made of SiN or other material.
- a resistance heating type heater 5 is embedded in the mounting table 2, and the heater 5 is heated by the heater power source 5a to heat the mounting table 2, and the heat is a substrate to be processed. Heat wafer W uniformly.
- the mounting table 2 is provided with a thermocouple 6 so that the heating temperature of the wafer W can be controlled, for example, in the range from room temperature to 900 ° C.
- the mounting table 2 has wafer support pins (not shown) for supporting the wafer W and raising and lowering it. It is provided so as to be able to project and retract with respect to the surface of the mounting table 2.
- a high frequency power supply 61 for bias is connected to the mounting table 2 via a matching circuit 60.
- the high frequency power supply 61 is configured to supply high frequency power of 1 to 500 W to the electrode 62 embedded in the mounting table 2 at a predetermined frequency such as 400 kHz to 27 MHz, specifically 400 kHz and 13.56 MHz. ing.
- the electrode 62 is formed, for example, in a mesh shape from a conductive material such as molybdenum or tungsten.
- a silicon nitride film having a strong compressive stress can be formed by supplying high-frequency power to the mounting table 2 with a predetermined output.
- annular gas introduction portions 15a and 15b are provided in two upper and lower stages, and each gas introduction portion 15a and 15b has a film forming source gas and A gas supply system 16 for supplying plasma excitation gas is connected.
- the gas introduction parts 15a and 15b may be arranged in a nozzle shape or a shower shape.
- the gas supply system 16 includes, for example, a nitrogen-containing gas supply source 17, a Si-containing gas supply source 18, and an inert gas supply source 19.
- the nitrogen-containing gas supply source 17 is connected to the upper gas introduction part 15a, and the Si-containing gas supply source 18 and the inert gas supply source 19 are connected to the lower gas introduction part 15b.
- Examples of the nitrogen-containing gas that is a film forming source gas include N, ammonia, and MMH (monomers).
- Tilhydrazine and the like can be used.
- Si-containing gas includes, for example, silane (SiH 2), disilane
- inert gas for example, N gas or rare gas can be used.
- Ar gas Kr gas, Xe gas, He gas, and the like can be used as the rare gas, which is a horra excitation gas.
- Ar gas is preferred.
- the nitrogen-containing gas reaches the gas introduction part 15a through the gas line 20, and is introduced into the chamber 11 from the gas introduction part 15a.
- the Si-containing gas and the inert gas reach the gas introduction part 15b through the gas lines 20, respectively, and are introduced into the chamber 11 from the gas introduction part 15b.
- Each gas line 20 connected to each gas supply source has a mass flow controller.
- An open / close valve 22 is provided at the front and rear of the valve 21 so that the gas supplied can be switched and the flow rate can be controlled.
- a rare gas for plasma excitation such as Ar is an arbitrary gas, and it is not always necessary to supply it simultaneously with the film forming source gas.
- An exhaust pipe 23 is connected to the side surface of the exhaust chamber 11, and the exhaust apparatus 24 including the high-speed vacuum pump is connected to the exhaust pipe 23. Then, by operating the exhaust device 24, the gas force in the chamber 11 is uniformly discharged into the space 11 a of the exhaust chamber 11 along the lower periphery of the mounting table 2 and exhausted through the exhaust pipe 23. As a result, the inside of the chamber 11 can be depressurized at a high speed to a predetermined degree of vacuum, for example, 0.133 Pa.
- a loading / unloading port 25 for loading / unloading the wafer W to / from a transfer chamber (not shown) adjacent to the plasma processing apparatus 100 and the loading / unloading port 25 are opened and closed.
- a gate valve 26 is provided!
- the upper portion of the chamber 11 is an opening, and an annular upper plate 27 is joined to the opening.
- An annular support portion 27a is formed at the inner peripheral lower portion of the upper plate 27 so as to project toward the inner space of the chamber.
- a dielectric such as quartz or Al 2 O 3 is formed on the support 27a.
- a microphone mouth wave transmitting plate 28 that is made of a ceramic such as A1N and transmits microwaves is airtightly provided via a seal member 29. Therefore, the inside of the chamber 1 is kept airtight.
- a disc-shaped planar antenna member 31 is provided above the transmission plate 28 so as to face the mounting table 2.
- the shape of the planar antenna member is not limited to a disk shape, and may be a square plate shape, for example.
- the planar antenna member 31 is locked to the upper end of the side wall of the chamber 11.
- the planar antenna member 31 is formed of, for example, a copper plate or aluminum plate force with a surface plated with gold or silver, and a plurality of slot-like microwave radiation holes 32 that radiate microwaves are formed in a predetermined pattern. It has been configured.
- the microwave radiation holes 32 form a pair, and the pair of microwave radiation holes 32 are typically arranged in a "T" shape, A plurality of these pairs are arranged concentrically.
- the length and arrangement interval of the microwave radiation holes 32 are determined according to the wavelength ( ⁇ g) of the microwaves in the waveguide 37.
- the microwave radiation holes 32 The spacing is arranged to be gZ4, gZ2 or g.
- the interval between adjacent microwave radiation holes 32 formed concentrically is indicated by Ar.
- the microwave radiation hole 32 may have another shape such as a circular shape or an arc shape.
- the arrangement form of the microwave radiation holes 32 is not particularly limited, and the microwave radiation holes 32 may be arranged concentrically, for example, spirally or radially.
- a slow wave member 33 having a dielectric constant larger than that of vacuum is provided on the upper surface of the planar antenna member 31.
- the slow wave material 33 has a function of adjusting the plasma by shortening the wavelength of the microwave because the wavelength of the microwave becomes longer in vacuum. It should be noted that the planar antenna member 31 and the transmission plate 28 and the slow wave member 33 and the planar antenna member 31 may be in close contact with each other or may be separated from each other. .
- a shield lid 34 made of a metal material such as aluminum or stainless steel is provided on the upper surface of the chamber 11 so as to cover the planar antenna member 31 and the slow wave member 33.
- the upper surface of the chamber 11 and the shield lid 34 are sealed by a seal member 35.
- a cooling water flow path 34a is formed in the shield lid 34, and cooling water is allowed to flow therethrough to cool the shield lid 34, the slow wave material 33, the planar antenna member 31, and the transmission plate 28. It has become.
- the shield lid 34 is grounded.
- An opening 36 is formed at the center of the upper wall of the shield lid 34, and a waveguide 37 is connected to the opening.
- a microwave generator 39 for generating microwaves is connected to the end of the waveguide 37 via a matching circuit 38. Thereby, for example, a microwave having a frequency of 2.45 GHz generated by the microwave generator 39 is propagated to the planar antenna member 31 through the waveguide 37.
- the microwave frequency 8.35 GHz, 1.98 GHz, or the like can be used.
- the waveguide 37 includes a coaxial waveguide 37a having a circular cross section extending upward from the opening 36 of the shield lid 34, and a mode converter 40 at the upper end of the coaxial waveguide 37a. And a rectangular waveguide 37b extending in the horizontal direction.
- the mode change 40 between the rectangular waveguide 37b and the coaxial waveguide 37a has a function of converting the microphone mouth wave propagating in the TE mode in the rectangular waveguide 37b into the TEM mode.
- An inner conductor 41 extends in the center of the coaxial waveguide 37a, and the inner conductor 41 is formed at the lower end of the planar antenna member 31. The connection is fixed at the center. Thereby, the microwave is efficiently and uniformly propagated radially and uniformly to the planar antenna member 31 through the inner conductor 41 of the coaxial waveguide 37a.
- Each component of the plasma processing apparatus 100 is connected to and controlled by a process controller 50 having a CPU.
- the process controller 50 has a user interface that also includes a keyboard for an operator to input commands for managing the plasma processing apparatus 100, a display for visualizing and displaying the operating status of the plasma processing apparatus 100, and the like. 51 is connected!
- the process controller 50 stores a control program (software) for realizing various processes executed by the plasma processing apparatus 100 under the control of the process controller 50, and a recipe in which processing condition data is recorded.
- the stored storage unit 52 is connected.
- the plasma processing is performed under the control of the process controller 50 by calling an arbitrary recipe from the storage unit 52 according to an instruction from the user interface 51 and causing the process controller 50 to execute it.
- the desired processing in apparatus 100 is performed.
- recipes such as the control program and processing condition data may be stored in a computer-readable storage medium such as a CD-ROM, a hard disk, a flexible disk, or a flash memory. For example, it is possible to transmit the data from time to time through a dedicated line and use it online.
- the plasma processing apparatus 100 configured in this way is capable of proceeding with damage-free plasma processing on the underlayer film, etc. at a low temperature of 800 ° C or lower, and is excellent in plasma uniformity. Uniformity can be realized.
- a silicon nitride film can be deposited on the surface of the wafer W by the plasma CV D method according to the following procedure.
- the gate valve 26 is opened, and the wafer W is loaded into the chamber 11 from the loading / unloading port 25 and mounted on the mounting table 2. Then, nitrogen-containing gas and silicon-containing gas from the nitrogen-containing gas supply source 17 and Si-containing gas supply source 18 of the gas supply system 16 are respectively supplied to the chamber 1 through the gas introduction portions 15a and 15b at predetermined flow rates. To introduce.
- the microwave from the microwave generator 39 is guided to the waveguide 37 through the matching circuit 38, and sequentially passes through the rectangular waveguide 37b, the mode converter 40, and the coaxial waveguide 37a. Then, the power is supplied to the planar antenna member 31 through the inner conductor 41, and the slot (microwave radiation hole 32) force of the planar antenna member 31 is also radiated to the space above the wafer W in the chamber 11 through the transmission plate 28.
- the microwave propagates in the TE mode in the rectangular waveguide 37b.
- the TE mode microwave is converted to the TEM mode by the mode change ⁇ 40, and the coaxial waveguide 37a is directed to the planar antenna member 31. Will be propagated.
- the microwave output at this time can be set to, for example, about 500 to 3000 kW.
- An electromagnetic field is formed in the chamber 11 by the microwaves radiated from the planar antenna member 31 through the transmission plate 28 to the chamber 11, and the nitrogen-containing gas and the silicon-containing gas are turned into plasma, respectively.
- the microwave-excited plasma has a high density of about 1 ⁇ 10 1G to 5 ⁇ 10 12 Zcm 3 by radiating microwaves from a number of slots (microwave radiation holes 32) of the planar antenna member 31.
- the low electron temperature plasma is about 1.5 eV or less. Since the microwave-excited plasma formed in this way has a high density with little plasma damage caused by ions etc.
- the source gas is in a highly dissociated state in the plasma, and SiH, NH, N, H, etc. Active species are generated, and a thin film of silicon nitride SixNy (where x and y are not necessarily stoichiometrically determined and take different values depending on conditions) is deposited by reaction between the active species. .
- a high frequency power of a predetermined frequency for example, 13.56 MHz, is supplied from the high frequency power supply 61 to the mounting table 2.
- activated species containing nitrogen such as NH and N + are easily drawn toward the wafer W.
- a silicon nitride film having extremely high compressive stress can be formed by changing the composition ratio of Si, N, and H and the density of these in the silicon nitride film.
- the plasma processing apparatus 100 has the advantage that it can maintain the low electron temperature of the plasma even when a bias is applied to the WENO and W by supplying high frequency power from the high frequency power supply 61 to the susceptor 2. Have it.
- the electron temperature of the plasma can be obtained from the voltage-current characteristics shown in Fig. 3 obtained by inserting a Langmuir probe into the plasma and sweeping the applied voltage. Specifically, the current value II is taken at an arbitrary position in the exponential function region of Fig. 3, and the current is multiplied by e (about 2. 7 times the voltage change ⁇ is the electron temperature (Te). Therefore, the electron temperature is the same if the slope of the exponential function region is the same.
- the voltage-current characteristic when plasma was generated by changing the high frequency bias applied to the susceptor was measured with a Langmuir probe.
- a 200 mm wafer was used, Ar gas was supplied at a flow rate of 250 mLZmin (sccm), the pressure was set to 7.3 Pa, the microwave power was set to 1000 W, and the bias power was changed to 0, 10, 30, and 50 W.
- the area of the electrode placed on the susceptor is 706.5 cm 2 .
- the results are shown in Fig. 4.
- the slope of the exponential region is almost constant regardless of the bias power, so the electron temperature also depends on the bias power (Figure 5 shows the bias power density) as shown in Figure 5. It was almost constant. That is, even if a high frequency bias is applied to the wafer W with a power density of 0.015 to lWZcm 2 , the low electron temperature characteristics of the plasma can be maintained.
- a silicon nitride film having a strong compressive stress without causing damage due to ions or the like. can be formed.
- the stress of the formed silicon nitride film is shifted to the compressive stress side by supplying high-frequency power to the mounting table 2. It becomes possible to make it.
- the stress shift width that is, the absolute value of the stress that changes due to the supply of high-frequency power, reaches 2000 MPa or more, for example, 3000 to 4500 MPa when the film forming conditions other than the application of high-frequency power are set to be the same.
- a silicon nitride film having a compressive stress can be formed regardless of the type of film forming material gas.
- NH gas when used as a nitrogen-containing gas, it is usually tensile stress A silicon nitride film is formed.
- a silicon nitride film having a strong compressive stress can be formed by performing film formation under RF bias conditions (that is, supplying high-frequency power to the mounting table 2). Therefore, it is effective to apply high-frequency power as one of the factors that control the strength and direction of stress (tension or compression).
- the power density (power per unit area) of the high-frequency power supplied to the mounting table 2 is 0.0043 to l to 500 WZcm 2 (for example, when the electrode area is 314 cm 2 ) regardless of the type of processing gas. 1 to 500 W) is preferable.
- the range of the high-frequency output for maximizing the compressive stress of the silicon nitride film varies depending on the processing pressure.
- NH gas as nitrogen-containing gas Si as silicon-containing gas
- the flow rate of NH gas is preferably 100 to 3000 mLZmin (sccm).
- Si H gas flow rate is l ⁇ 30mL / min (sccm)
- N as a nitrogen-containing gas
- N gas flow rate is
- the volume is set to 1-30 mLZmin (sccm), preferably 4-15 mLZmin (sccm).
- sccm mLZmin
- sccm mLZmin
- Si H gas Si-containing gas
- the processing pressure is set to, for example, not less than 0.1 Pa and not more than 53 Pa.
- the processing pressure In order to form a silicon nitride film having a compressive stress of 2000 MPa or more, it is preferable to set the processing pressure to, for example, 0.1 Pa or more and 40 Pa or less.
- the processing pressure in order to form a silicon nitride film having a compressive stress of 3000 MPa or more, it is preferable to set the processing pressure to, for example, 5 Pa or more and 25 Pa or less. 016-0. 127 WZcm 2 is preferable. For example, when the electrode area is 314 cm 2 , the high frequency power is 5 to 40W.
- the processing pressure in order to form a silicon nitride film having a compressive stress of 3500 MPa or more, it is preferable to set the processing pressure to, for example, 7 Pa or more and 16 Pa or less. It is preferable to set to 0.032 to 0.096 WZcm 2 . For example, when the electrode area is 314 cm 2 , the high frequency power is 10-30W.
- the mounting table 2 is set to 300 ° C or higher, preferably 400 to 800. Heating to ° C is preferred.
- the gap in the plasma processing apparatus 100 (the bottom surface force of the transmission plate 28 is also the distance to the top surface of the mounting table 2).
- a strong compressive stress can be applied to the silicon nitride film by using the plasma processing apparatus 100 and selecting the plasma C VD conditions while supplying the RF bias.
- the magnitude of stress can be controlled by changing the processing pressure.
- FIG. 6 is a schematic cross-sectional view showing a schematic configuration of a transistor 200 having a MOS (Meta-Oxide-silicon) structure.
- a gate electrode 103 made of, for example, polysilicon is formed on a P-type or N-type Si layer 101 with a gate insulating film 102 interposed therebetween.
- a source 104 and a drain 105 are formed on both sides below the gate electrode 103, and a channel region 106 (shaded portion in FIG. 6) is formed between them.
- a covering film (liner) 107 made of an insulating film is formed so as to cover the gate electrode 103.
- the coating film 107 can be formed by plasma CVD using the plasma processing apparatus 100. At that time, by controlling the plasma CVD conditions, as described above, tensile stress or compressive stress can be applied to the coating film 107. In particular, it is possible to form a silicon nitride film having a strong compressive stress by selecting the RF bias condition and the processing pressure.
- the coating film 107 is subjected to stress in the direction indicated by the black arrow 108 in FIG. Then, tensile stress in the same direction as the black arrow 108 is applied to the silicon constituting the source 104 and the drain 105 in contact with the coating film 107. As a result, tensile stress in the same direction as the black arrow 108 is also applied to the channel region 106, and tensile strain occurs in the channel region 106.
- the transistor 200 When the transistor 200 is an NMOS transistor using electrons as carriers, the mobility increases when tensile strain is applied to the channel region 106, but the mobility decreases when compressive strain is applied. On the other hand, when the transistor 200 is a PMOS transistor using holes as carriers, the mobility increases when compressive strain is applied to the channel region 106, and the mobility decreases when tensile strain is applied.
- the transistor 200 when the transistor 200 is an NMOS transistor, a saturation driving current value or linearity is obtained by using a silicon nitride film having a tensile stress as the covering film 107 and generating a tensile strain in the channel region 106.
- the drive current value can be increased.
- a silicon nitride film having a compressive stress is used as the covering film 107, and a compressive strain is generated in the channel region 106, so that a saturation driving current value or a linear driving current value can be obtained.
- the driving performance of the transistor 200 can be improved by using a silicon nitride film having a tensile stress or a compressive stress as the coating film 107.
- a silicon nitride film having stress is applied to the coating film 107, but other than this, for example, silicon nitride having stress is used as a sidewall formed on both sides of the gate electrode 103.
- a membrane can be used.
- the transistor 200 can be manufactured, for example, by using the plasma processing apparatus 100 to form the coating film 107 that covers the gate electrode 103 under the condition that a tensile stress or a compressive stress can be applied.
- 7A-7B illustrate the plasma of the present invention as part of the manufacturing process of transistor 200. It is drawing explaining the example which applied the CVD method.
- the transistor structure shown in FIG. 7A can be formed by the following procedure. First, a well (not shown) is formed on the P-type or N-type Si layer 101, and an element isolation layer (not shown) is formed by, for example, the LOCOS method or STI (Shallow Trench Isolation). Next, a gate insulating film 102 such as a silicon nitride film or a silicon oxide film is formed on the surface of the Si layer 101 by a method such as plasma treatment or heat treatment. A polysilicon layer is formed on the gate insulating film 102 by CVD, for example, and then etched based on a mask pattern formed by a photolithography technique to form a gate electrode 103.
- a well is formed on the P-type or N-type Si layer 101
- an element isolation layer is formed by, for example, the LOCOS method or STI (Shallow Trench Isolation).
- a gate insulating film 102 such as a silicon nitride film or a silicon oxide film is formed
- the gate electrode structure is not limited to a single polysilicon layer, and for the purpose of reducing the specific resistance of the gate electrode and increasing the speed, for example, tungsten, molybdenum, tantalum, titanium, conoretol, nickel, their silicides, A laminated structure including a nitride, an alloy, or the like can also be used.
- ion implantation and active ion treatment are performed to form the source 104 and the drain 105.
- a silicon nitride film is formed using plasma processing apparatus 100 so as to cover the surface of Si layer 101 and gate electrode 103.
- a silicon nitride film having a strong compressive stress can be formed by causing a film forming reaction while supplying high-frequency power to the mounting table 2.
- a MOS structure transistor 200 can be manufactured as shown in FIG. 7C. it can.
- annealing can be performed as necessary.
- the CMOS transistor 300 shown in FIG. 8 When the CMOS transistor 300 shown in FIG. 8 is manufactured, film formation, patterning by photolithography, etching, and the like are sequentially performed to form the NMOS region 201 and the PMOS region 202, and further, By forming and etching the silicon nitride film under the film forming conditions that can apply the tensile stress or compressive stress of the invention, the coating films 203 and 204 can be formed in the NMOS region 201 and the PMOS region 202, respectively. .
- a p-type well 211 that becomes the NMOS region 201 and an n-type well 212 that becomes the PMOS region 202 are formed on the silicon substrate 210.
- a gate electrode 214 which is also poly-S, is formed on the main surface of the p-type well 211 via a gate insulating film 213, and a source 215 and a drain 216 are formed on both sides of the gate electrode 214.
- the sidewall of the gate electrode 214 is Form all 217.
- a gate electrode 224 made of poly-Si is formed on the main surface of the n-type well 212 via a gate insulating film 213, and a source 225 and a drain 226 are formed on both sides of the gate electrode 224.
- a side wall 227 is formed on the side wall of the gate electrode 224.
- Reference numeral 230 denotes an element isolation region. The procedure at this time is in accordance with FIGS. 7A to 7C.
- a tensile stress silicon nitride film is deposited on the entire surface using the plasma processing apparatus 100, and the tensile stress is applied from the PMOS region 202 by etching.
- the silicon nitride film is removed, and only the NMOS region 201 is left with a covering film 203 made of a tensile stressed silicon nitride film.
- a compressive stress silicon nitride film is deposited on wafer W using plasma processing apparatus 100. Then, the compressive stress silicon nitride film is removed from the NMOS region 201 by etching, and the coating film 204 made of the compressive stress silicon nitride film is left only in the PMOS region. In this manner, in each of the NMOS region 201 and the PMOS region 202, the stress of the silicon nitride film is used to cause tensile strain in the channel region 218 of the NMOS region 201, and in the channel region 228 of the PMOS region 202. It is possible to manufacture a CMOS transistor with improved performance by generating compressive strain.
- the silicon nitride film formed by plasma CVD using the plasma processing apparatus 100 can also be applied to the nonvolatile memory 400 as shown in FIG.
- a tunnel oxide film 302 is formed on the main surface of the Si substrate 301, and a floating gate (FG) 304 force made of polysilicon is formed thereon.
- FG floating gate
- CG control gate
- An insulating layer 307 is formed on 306, sidewall oxide films 308 are formed on the sidewalls of the floating gate 304 and the control gate 306 by oxidation treatment, and the source is formed on both sides of the floating gate 304 on the main surface of the Si substrate 301. 309 and drain 310 are formed, and stress is applied to cover the floating gate 304, the control gate 306, the source 309, and the drain 310.
- Coating film 311 is made form consisting of. [0074] By forming a stressed silicon nitride film as the abdominal membrane 311 in this way, it is possible to give an appropriate strain to the floating gate 304.
- the charge of the floating gate 304 is lost by tunneling to the Si substrate through the tunnel oxide film (tunnel current), but the memory is lost.
- tunnel current tunnel current
- the average electron mass and the barrier width of the SiO that composes the tunnel oxide film 302 increase, so the tunnel current is reduced and the flow is reduced.
- the single gate 304 can hold the charge more stably.
- FIG. 10 is a graph showing the relationship between the stress level of the silicon nitride film and the processing pressure in the plasma C VD in the plasma processing apparatus 1.
- film formation is performed without supplying high-frequency power to the mounting table 2 in order to investigate the effects of the gas type and pressure.
- the vertical axis in FIG. 10 indicates the magnitude of stress in the silicon nitride film, the positive (plus) side is tensile stress, and the negative (minus) side is compressive stress (the same applies to FIGS. 11 to 15). is there).
- the silicon nitride film was formed under the following plasma CVD conditions.
- the silicon nitride film formed by using NH as the nitrogen-containing gas is
- a silicon nitride film formed using N as the nitrogen-containing gas has a compressive stress.
- the compressive stress of the silicon nitride film formed using N is low in processing pressure.
- Microwave power 2000W RF frequency: 400kHz
- the base film should have tensile stress under normal film formation conditions, it was confirmed that the film had a large compressive stress when it was formed under the prescribed RF bias conditions.
- N / Si H-based gas is used as the film forming source gas, and the compression gas is used even under normal film forming conditions.
- the compressive stress is enhanced by forming the film under a predetermined RF bias condition.
- the silicon nitride film is used regardless of whether the source material is N H / Si H type gas or N / Si H type gas.
- a silicon nitride film having a compressive stress of lOOOMPa or more is formed.
- the electrode area is 314 cm 2
- a silicon nitride film with a strong compressive stress of 2000 MPa or more is formed when the RF power is in the range of 20 to 40W. Therefore, the RF bus Iasu conditions, RF power density is 0.032 to 0. Range 637WZcm 2 is preferred, 0. 064-0. 127WZcm 2 (but it was confirmed more preferred.
- a compressive-stressed silicon nitride film can be formed regardless of the type of film source gas.
- the RF noise condition under which the compressive stress was greatest was about 0.095 WZcm 2 (electrode area: 314 cm 2 , RF power: about 30 W) in terms of power density. Therefore, it is considered that the high frequency power supplied to the mounting table 2 is preferably 0.1 to L00W, more preferably 0.1 to 40W. In other words, it is preferable to set the power range so that the power density is such that a large compressive stress can be obtained according to the electrode area.
- Processing pressure 2. 67Pa (20mTorr), 13.3Pa (100mTorr) and 66.6Pa (500mTorr)
- RF power 0 W (not supplied), 10 W (power density: 0. 032WZcm 2), 20W (power density: 0. 064WZcm 2), 30W (power density: 0. 095WZcm 2), 50W (power density: 0. 159W / cm 2 )
- Si H gas flow rate 3 or 5mLZmin (sccm)
- Processing pressure 2. 67Pa (20mTorr), 13.3Pa (100mTorr) and 66.6Pa (500mTorr)
- RF power 0 W (not supplied), 10 W (power density: 0. 032WZcm 2), 20W (power density: 0. 064WZcm 2), 30W (power density: 0. 095WZcm 2), 50W (power density: 0. 159W / cm 2 )
- Figures 12 and 13 show the results for the N / Si H system
- Fig. 14 shows the results for the NH / Si H system.
- the processing pressure may be set to, for example, 0.1 Pa or more and 53 Pa or less. Further, it can be seen that the processing pressure may be set to, for example, 0.1 Pa or more and 40 Pa or less in order to form a silicon nitride film having a compressive stress of 2000 MPa or more. Furthermore, it can be seen that in order to form a silicon nitride film having a compressive stress of 3000 MPa or more, the processing pressure may be set to 5 Pa or more and 25 Pa or less, for example.
- the high frequency power may be 5 to 40 W.
- the processing pressure should be set to, for example, 7 Pa or more and 16 Pa or less, and the high frequency power in this case may be 10 to 30 W.
- the power density of high frequency for bias, 0. 016-0. 127WZcm 2 is preferred tool 0. 032 ⁇ 0. 095W / cm 2 preferred than force! / ⁇
- the processing pressure is 13.3 Pa (100 mTorr)
- the RF power density is as strong as 3500 MPa at about 0.032 to 0.095 W / cm 2 (RF power: 10 to 30 W).
- a compressive stress silicon nitride film could be formed.
- the processing pressure is 2.67 Pa (20 mTorr)
- a silicon nitride film with a compressive stress exceeding 2000 MPa with an RF power density of about 0.095 to 0.127 WZcm 2 (RF power: 30 to 40 W) is used. I was able to form.
- the processing pressure was 66.6 Pa (500 mTorr)
- compressive stress could not be applied to the silicon nitride film even when high-frequency power was supplied.
- the influence of the frequency of the high frequency power supplied to the mounting table 2 was examined.
- the RF pressure density is changed when the processing pressure is 13.3 Pa (100 mTorr) and the frequency of the high-frequency power supplied to the mounting table 2 is 400 kHz and 13.56 MHz.
- the stress of the silicon nitride film was measured. The results are shown in Fig. 15. From this figure, it was confirmed that the compression stress was greater at 13.56 MHz.
- the film forming conditions and annealing conditions are as follows.
- Processing time 10 minutes, 20 minutes or 30 minutes
- FIG. 16 shows the relationship between the stress of the silicon nitride film and the annealing time. From Fig. 16, it is shown that nitridation with compressive stress formed under the above conditions using Si H and N as source gases.
- the silicon film is a silicon nitride film with compressive stress formed using Si H and NH under the above conditions.
- the fluctuation range of stress before and after annealing was remarkably small, and it was confirmed that the film was excellent in heat resistance. From this result, Si H and N are used as source gases in plasma CVD.
- the silicon nitride film has excellent resistance while maintaining high stress against repeated heat treatment in the manufacturing process of various semiconductor devices It became clear that
- a silicon nitride film having a tensile stress or a compressive stress is applied to a covering film (liner) of a transistor to improve driving characteristics
- the present invention is not limited thereto. It can also be applied to the manufacture of various semiconductor devices that can improve device characteristics using stress.
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Abstract
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US12/302,614 US8114790B2 (en) | 2006-05-31 | 2007-05-30 | Plasma CVD method, silicon nitride film formation method, semiconductor device manufacturing method, and plasma CVD apparatus |
KR1020087029276A KR101063083B1 (ko) | 2006-05-31 | 2007-05-30 | 플라즈마 cvd 방법, 질화 규소막의 형성 방법, 반도체 장치의 제조 방법 및 플라즈마 cvd 장치 |
JP2008517961A JP5341510B2 (ja) | 2006-05-31 | 2007-05-30 | 窒化珪素膜の形成方法、半導体装置の製造方法およびプラズマcvd装置 |
CN2007800191810A CN101454880B (zh) | 2006-05-31 | 2007-05-30 | 等离子体cvd方法、氮化硅膜的形成方法、半导体装置的制造方法和等离子体cvd装置 |
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PCT/JP2007/060976 WO2007139142A1 (ja) | 2006-05-31 | 2007-05-30 | プラズマcvd方法、窒化珪素膜の形成方法、半導体装置の製造方法およびプラズマcvd装置 |
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US (1) | US8114790B2 (ja) |
JP (1) | JP5341510B2 (ja) |
KR (1) | KR101063083B1 (ja) |
CN (1) | CN101454880B (ja) |
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WO2009123325A1 (ja) * | 2008-03-31 | 2009-10-08 | 東京エレクトロン株式会社 | 窒化珪素膜の製造方法、窒化珪素膜積層体の製造方法、コンピュータ読み取り可能な記憶媒体およびプラズマcvd装置 |
WO2009123331A1 (ja) * | 2008-03-31 | 2009-10-08 | 東京エレクトロン株式会社 | Mos型半導体メモリ装置およびその製造方法 |
WO2009123335A1 (ja) * | 2008-03-31 | 2009-10-08 | 東京エレクトロン株式会社 | Mos型半導体メモリ装置の製造方法およびプラズマcvd装置 |
JP2009246210A (ja) * | 2008-03-31 | 2009-10-22 | Tokyo Electron Ltd | 窒化珪素膜の製造方法、窒化珪素膜積層体の製造方法、コンピュータ読み取り可能な記憶媒体およびプラズマcvd装置 |
WO2010038886A1 (ja) * | 2008-09-30 | 2010-04-08 | 東京エレクトロン株式会社 | 窒化珪素膜の成膜方法、コンピュータ読み取り可能な記憶媒体およびプラズマcvd装置 |
US8119545B2 (en) | 2008-03-31 | 2012-02-21 | Tokyo Electron Limited | Forming a silicon nitride film by plasma CVD |
JP2012510712A (ja) * | 2008-08-29 | 2012-05-10 | アドバンスト・マイクロ・ディバイシズ・インコーポレイテッド | 同一の能動領域内に形成されるトランジスタにおいて能動領域内に局所的に埋め込み歪誘起半導体材質を設けることによる駆動電流調節 |
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CN101454880A (zh) | 2009-06-10 |
KR20090005405A (ko) | 2009-01-13 |
TW200807511A (en) | 2008-02-01 |
CN101454880B (zh) | 2012-05-02 |
KR101063083B1 (ko) | 2011-09-07 |
US20090203228A1 (en) | 2009-08-13 |
JP5341510B2 (ja) | 2013-11-13 |
US8114790B2 (en) | 2012-02-14 |
JPWO2007139142A1 (ja) | 2009-10-08 |
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