WO2005078784A1 - シリコン酸化膜の製造方法 - Google Patents
シリコン酸化膜の製造方法 Download PDFInfo
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- WO2005078784A1 WO2005078784A1 PCT/JP2005/002425 JP2005002425W WO2005078784A1 WO 2005078784 A1 WO2005078784 A1 WO 2005078784A1 JP 2005002425 W JP2005002425 W JP 2005002425W WO 2005078784 A1 WO2005078784 A1 WO 2005078784A1
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- Prior art keywords
- silicon oxide
- film
- oxide film
- reactor
- producing
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000004065 semiconductor Substances 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 239000003085 diluting agent Substances 0.000 claims description 6
- 238000002230 thermal chemical vapour deposition Methods 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 9
- 229910000077 silane Inorganic materials 0.000 abstract description 6
- -1 silane compound Chemical class 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 86
- 239000000758 substrate Substances 0.000 description 27
- 239000007789 gas Substances 0.000 description 26
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 19
- AKYUXYJGXHZKLL-UHFFFAOYSA-N triethoxy(triethoxysilyl)silane Chemical compound CCO[Si](OCC)(OCC)[Si](OCC)(OCC)OCC AKYUXYJGXHZKLL-UHFFFAOYSA-N 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 239000001307 helium Substances 0.000 description 15
- 229910052734 helium Inorganic materials 0.000 description 15
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 238000000862 absorption spectrum Methods 0.000 description 7
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 230000021615 conjugation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WDFIBGBTIINTHZ-UHFFFAOYSA-N CCO[SiH2][SiH3] Chemical compound CCO[SiH2][SiH3] WDFIBGBTIINTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- VRPCJDJBSZOJFF-UHFFFAOYSA-N propoxy(silyl)silane Chemical compound CCCO[SiH2][SiH3] VRPCJDJBSZOJFF-UHFFFAOYSA-N 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- MZIJWTNDBFXVFP-UHFFFAOYSA-N CCCCO[SiH](OCCCC)[Si](OCCCC)(OCCCC)OCCCC Chemical compound CCCCO[SiH](OCCCC)[Si](OCCCC)(OCCCC)OCCCC MZIJWTNDBFXVFP-UHFFFAOYSA-N 0.000 description 1
- KDCKNAMXPYLGIW-UHFFFAOYSA-N CCO[Si]([SiH3])(OCC)OCC Chemical compound CCO[Si]([SiH3])(OCC)OCC KDCKNAMXPYLGIW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- QKEZLXNZVHUFGN-UHFFFAOYSA-N butoxy(silyl)silane Chemical compound CCCCO[SiH2][SiH3] QKEZLXNZVHUFGN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KJVWTDGLSMEVAP-UHFFFAOYSA-N diethoxysilyl(triethoxy)silane Chemical compound CCO[SiH](OCC)[Si](OCC)(OCC)OCC KJVWTDGLSMEVAP-UHFFFAOYSA-N 0.000 description 1
- GGMZTHUSWCBELM-UHFFFAOYSA-N dimethoxy(silyl)silane Chemical compound CO[SiH]([SiH3])OC GGMZTHUSWCBELM-UHFFFAOYSA-N 0.000 description 1
- LKVRRCHKYMPJJR-UHFFFAOYSA-N dimethoxysilyl(trimethoxy)silane Chemical compound CO[SiH](OC)[Si](OC)(OC)OC LKVRRCHKYMPJJR-UHFFFAOYSA-N 0.000 description 1
- GGGKIJXKLAIXIF-UHFFFAOYSA-N dipropoxysilyl(tripropoxy)silane Chemical compound CCCO[SiH](OCCC)[Si](OCCC)(OCCC)OCCC GGGKIJXKLAIXIF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- MEBNNDGCPRQQBQ-UHFFFAOYSA-N methoxy(silyl)silane Chemical compound CO[SiH2][SiH3] MEBNNDGCPRQQBQ-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229960001730 nitrous oxide Drugs 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000012771 pancakes Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- RTJCZMGWCRHRTD-UHFFFAOYSA-N tributoxy(tributoxysilyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)[Si](OCCCC)(OCCCC)OCCCC RTJCZMGWCRHRTD-UHFFFAOYSA-N 0.000 description 1
- WYSYKUDDULIZNW-UHFFFAOYSA-N trimethoxy(silyl)silane Chemical compound CO[Si]([SiH3])(OC)OC WYSYKUDDULIZNW-UHFFFAOYSA-N 0.000 description 1
- LMQGXNPPTQOGDG-UHFFFAOYSA-N trimethoxy(trimethoxysilyl)silane Chemical compound CO[Si](OC)(OC)[Si](OC)(OC)OC LMQGXNPPTQOGDG-UHFFFAOYSA-N 0.000 description 1
- MKISSKFQCNKIFR-UHFFFAOYSA-N tripropoxy(tripropoxysilyl)silane Chemical compound CCCO[Si](OCCC)(OCCC)[Si](OCCC)(OCCC)OCCC MKISSKFQCNKIFR-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- H01L21/02109—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
- H01L21/02164—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 oxide, e.g. SiO2
-
- 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
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
-
- 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
- H01L21/02205—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
- H01L21/02214—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 comprising silicon and oxygen
- H01L21/02216—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 comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
-
- 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
-
- 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]
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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
- H01L21/04—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
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
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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
- H01L21/04—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
Definitions
- the present invention provides an efficient method for manufacturing a silicon oxide film widely applied to the manufacture of semiconductor devices.
- the present invention relates to a method for manufacturing a semiconductor device in which an insulating film made of a silicon oxide film is formed by a CVD method.
- a method for producing a silicon oxide film As a method for producing a silicon oxide film, a method of forming a silicon oxide film using a monosilane gas and oxygen as a raw material gas by a thermal chemical vapor deposition method and the like have been known, but recently, because of poor step coverage, these methods have recently been used. A method of using an organic silane gas such as tetraethoxysilane and ozone as raw materials has been studied.
- Silicon oxide films are manufactured by a thermal chemical vapor deposition method, a photochemical vapor deposition method, a plasma chemical vapor deposition method, or the like.
- the thermal chemical vapor deposition method requires a high temperature to decompose or react the raw material by heat, which limits the types of substrates on which the film can be deposited, and the photochemical vapor deposition method forms the film at a low temperature.
- the window for introducing light is cloudy. In the case of ⁇ ⁇ , the film formation rate was low, and there was a problem in the production efficiency.
- Silane conjugation products such as monosilane conjugation products and disilane conjugation products are used for various applications.
- silane conjugates are often used as raw materials for manufacturing silicon-based insulating films such as silicon nitride, silicon oxide, and silicon oxynitride by a CVD method.
- the silani conjugate has a silicon nitride by reacting with a nitrogen-containing reaction gas such as ammonia, a silicon oxide by reacting with an oxygen-containing gas such as oxygen, and a reaction between a nitrogen-containing gas and an oxygen-containing gas.
- a nitrogen-containing reaction gas such as ammonia
- oxygen-containing gas such as oxygen
- a standard method for producing a silicon oxide hydride by a CVD method includes a reaction of oxidizing a SiH4 gaseous material as a silicon hydride with O, but in recent years, a minimum installation of a semiconductor device has been proposed.
- the thickness of the silicon oxide film has reached the stage where it can be counted by the number of atomic layers due to the high integration of the dimensional force, and the problem of thermal load has been raised with the miniaturization of the element structure. There is a demand for a low-temperature process that can reduce the temperature.
- TEOS reaction of oxidizing with O using a run
- films grown by CVD using TEOS still have problems in film quality such as denseness, crack resistance, and insulating properties. Requires substrate heating of one 700 ° C. Therefore, when the Si02 film is formed on the aluminum wiring by the CVD method using TEOS, there is a disadvantage that the aluminum wiring is significantly deteriorated.
- a method of forming a silicon oxide film by reacting alkoxysilane and oxygen by low-pressure plasma chemical vapor deposition is also known.
- a thin film can be formed at a low temperature, and heat resistance can be reduced.
- the film forming temperature which is said to be suitable in this method, is low. The temperature was about 350 ° C. to about 400 ° C., and the silicon oxide film having the formed force was not necessarily satisfactory because of its flatness and film quality.
- an oxide silicon film is formed by a CVD method in which an organic alkoxysilane containing one or more linear siloxane bonds is reacted with ozone.
- a method of forming a substrate on a substrate for example, Patent Document 1.
- Patent Document 1 JP-A-7-142578
- the present inventors have proposed a silicon oxide that can provide a sufficient film forming rate at a low temperature, has uniform film quality, has good step coverage, has excellent flatness, is low in cost, and has no problem in terms of safety.
- An object of the present invention is to provide a method for manufacturing a film.
- the present invention provides a method for manufacturing a semiconductor device for forming a Si02 insulating film having better film quality than TEOS at a low temperature.
- the present invention uses, as a raw material gas, a silane conjugate represented by the following general formula together with a diluent gas, at a pressure of 0.1 OlmmHg-2 atm, by a thermal chemical vapor deposition method or a plasma chemical vapor deposition method. Forming a silicon oxidized film by the method described above.
- R is an alkyl group having 16 carbon atoms, and n is an integer of 0-5.
- the silicon oxide film can be obtained at a low film forming rate at a low temperature, and therefore, it can be applied to a wide range of base materials including a base material to be processed at a low temperature.
- the resulting film is uniform, has excellent flatness, and has good step coverage.
- an insulating film in a semiconductor device can be obtained at a low deposition temperature.
- FIG. 1 shows an infrared absorption spectrum of the film obtained in Example 7.
- the raw material alkoxydisilane is a compound represented by the following general formula.
- R is an alkyl group having 16 carbon atoms
- n is an integer of 0 to 5.
- monoalkoxydisilane, dialkoxydisilane, trialkoxydisilane, tetraalkoxydisilane, pentaalkoxy examples thereof include disilane and hexalkoxydisilane.
- Preferred compounds are those in which n in the above formula is 2 or less. Examples of preferred disilane compounds are tetraalkoxydisilane and hexaalkoxydisilane, and particularly preferred compounds are hexaalkoxydisilane.
- the alkoxydisilane those having an alkoxy group having a carbon number of 16 are preferable, and an ethoxy group is particularly preferable.
- alkoxydilan examples include monomethoxydisilane, monoethoxydisilane, monopropoxydisilane, monobutoxydisilane, and other monoanorecoxydisilane, dimethoxydisilane, ethoxydisilane, propoxydisilane, dibutoxydisilane, and the like.
- Dianolecoxy disilane trimethoxydisilane, triethoxydisilane, tripropoxydisilane, tribubutoxydisilane, etc., trianolecoxydisilane, tetramethoxydisilane, tetraethoxydisilane, tetrapropoxydisilane, tetrabutoxydisilane, etc.
- Pentaalkoxydisilanes such as disilane, pentamethoxydisilane, pentaethoxydisilane, pentapropoxydisilane, and pentabutoxydisilane; hexamethoxydisilane; Saetoki Shijishiran, the hexa propoxy disilane, Kisaanorekoki Shijishiran the like to the like hexa-butoxy disilane to.
- tetraethoxydisilane and hexethoxydisilane are more preferred, and hexethoxydisilane is most preferred.
- the alkoxydisilane is bubbled with a diluent gas and vaporized to be supplied into the reaction system, or it is generally vaporized by heating and supplied together with the diluent gas.
- the diluent gas used for supplying the alkoxydisilane and present in the reaction system includes rare gases such as helium, neon, argon, krypton, and xenon, and nitrogen and hydrogen. No.
- the diluent gas is preferably at least 50 vol%, particularly preferably 80 vol% to 99 vol%, of the total gas amount in the reaction system including the source gas. If it is less than 50 vol%, the plasma may not stand stably and the film quality may be degraded.
- the pressure in the reaction system needs to be 0. OlmmHg-2 atm. If it is less than 0.lmmHg, an ultra-vacuum evacuation system is required. And costly problems occur.
- the preferred pressure is 0.1 OlmmHg-800 mmHg, and the more preferred pressure is 0.1 ImmHg-800 mmHg.
- the presence of an oxidizing agent in the reaction system makes it possible to produce a denser film at a lower temperature.
- the oxidizing agent is preferably 0.5 mol-50 mol force S per 1 mol of alkoxydisilane. If the amount is less than 0.5 mol, dense film quality may not be obtained. If the amount is more than 50 mol, fine particles of silicon oxide are likely to be generated by a gas phase reaction, and the film quality is deteriorated. As for the cost, the efficiency of the membrane becomes worse, and it is not economical.
- the oxidizing agent is generally introduced into the system together with the raw material gas, but may be separately introduced into the system.
- Examples of the substrate on which a silicon oxide film is formed according to the present invention include a semiconductor element such as a semiconductor substrate or an electrode wiring.
- the material is not limited to silicon, glass, aluminum, stainless steel, etc., and of course, since the present invention can form a film at a low temperature, non-quality such as amorphous silicon, and resin such as polyester, polyimide, glass epoxy, etc. Suitable substrates are obtained. Further, the shape of the substrate is not particularly limited.
- the temperature for forming the silicon oxide film on the substrate is as low as 200 ° C to 500 ° C. If it is less than 200, the film quality may be deteriorated.
- the specific film formation temperature can be appropriately selected depending on the source gas. For example, when hexethoxydisilane is used, 200 ° C-300 ° C is more preferred.
- the reaction apparatus used in the present invention is not particularly limited, and examples thereof include a vertical type, a horizontal type, a pancake type, a belt conveyor type, and a winding type.
- an electrode to which a high voltage is applied and an electrode to be grounded are arranged in a reactor, and an apparatus capable of forming a film at a pressure of 0.1 OlmmHg-2 atm. It is not particularly limited. Further, when the base material is a metal or the like near the atmospheric pressure, an arc discharge is generated by applying a high voltage, and it is somewhat difficult to form a silicon oxide film by exciting plasma of alkoxydisilane. In this case, it is preferable to use an electrode device in which a heat-resistant solid dielectric such as glass, ceramics, or plastics is placed on the electrode to which a high voltage is applied, so that the electrode can be sufficiently applied. .
- the oscillation frequency may be appropriately selected from a low frequency of 50Hz to 60Hz to a high frequency of 13.56MHz, 27MHz, and 2.45GHz or more.
- Hexethoxydisilane As a preferred silane compound represented by the above general formula, there is hexethoxydisilane.
- Hexethoxydisilane has a structure in which six ethoxy groups are attached to two Si, and is colorless and transparent at room temperature. Liquid.
- the heating temperature of the substrate in CVD is usually 300-500 ° C.
- the present invention is applicable to the manufacture of a liquid crystal semiconductor device formed on a glass substrate.
- a good silicon oxide film can be formed at a low temperature.
- the silicon oxide film formed according to the present invention is useful as an interlayer insulating film, a protective film, a mask material, a gaseous monolayer film and the like.
- a SiO film was formed by atmospheric pressure ozone CVD using hexethoxydisilane. Film formation
- N was used as a blanket gas at 0.5 slm, and the substrate temperature was 300 ° C.
- the pressure in the reactor was set to 760 mmHg, and the reaction was performed for 10 minutes to form a 0.22 m-thick film.
- the electric field strength at this time is 7MVcm 1
- the leakage current is 10- 8 A 'cm 2 or less
- the withstand voltage is LOMVcm 1 becomes, the silicon Sani ⁇ , best quality is obtained high temperature thermal oxidation
- the film quality was equivalent to the dielectric withstand voltage of 8 ⁇ 1 lMVcm 1 .
- a film having a thickness of 0.10 m was formed in the same manner as in Example 1 except that TEOS was used instead of hexethoxydisilane.
- a cylindrical quartz reactor 200111111 () 10011111111
- a silicon substrate (3 inch ⁇ ) was placed on a susceptor in the reactor, and the substrate was heated at 400 ° C. by heat.
- Hexethoxydisilane heated to 80 ° C was bubbled with helium at a flow rate of lOOmlZmin (corresponding to a supply of 0.27mlZmin as hexethoxydisilane), and was placed in the above device together with 2000mlZmin of helium and oxygen of 10mlZmin. Introduced.
- the pressure in the reactor was set to 760 mmHg, and the reaction was performed for 10 minutes to form a film having a thickness of 0.12 ⁇ m.
- the obtained film was uniform and excellent in flatness, and as a result of measurement by an infrared absorption spectrum, it was found that the film was a silicon oxide film and no organic components such as ethoxy groups and ethyl groups remained. Was.
- Example 2 The same procedure as in Example 2 was carried out except that the raw material gas was monosilane and monosilane lOmlZmin was introduced into the apparatus together with helium 2000 mlZmin and oxygen lOOmlZmin.As a result, generation of fine particles was observed in the reaction apparatus, and Had a slight, rough and undulating surface, though partially.
- Example 2 Using the reaction apparatus used in Example 2, a silicon substrate (3 inches ⁇ ) was placed on a susceptor and heated and maintained at 400 ° C. [0045] The raw material was prepared in the same manner as in Example 2 except that hexane ethoxydisilane heated to 80 ° C was bubbled with helium at a flow rate of lOOmlZmin (corresponding to 0.27mlZmin as hexethoxydisilane). Gas, helium and oxygen were introduced into the device.
- lOOmlZmin corresponding to 0.27mlZmin as hexethoxydisilane
- the pressure in the reactor was adjusted to 10 mmHg, and the reaction was carried out for 10 minutes to form a film having a thickness of 0.06 ⁇ m.
- the obtained film was uniform and excellent in flatness, and as a result of measurement by an infrared absorption spectrum, it was found that the film was a silicon oxide film and no organic components such as ethoxy group and ethyl group remained.
- the film was a silicon oxide film and no organic components such as ethoxy group and ethyl group remained.
- Example 3 The procedure was as in Example 3, except that the source gas was monosilane and monosilane lOmlZmin was introduced into the reactor together with helium 2000 mlZmin and oxygen lOOmlZmin.As a result, the generation of fine particles was observed in the reactor, but the film formed. It was a powerful force.
- the distance between the electrodes was 10 mm. Silicon substrate (3 inch) on the susceptor in the reactor
- Hexethoxydisilane heated to 80 ° C is bubbled with helium at a flow rate of lOOmlZmin (corresponding to a supply of 0.27mlZmin as hexethoxydisilane) and 2,000ml of helium.
- the pressure in the reactor was set to 0.1 mmHg, a glow discharge was generated at a high frequency of 13.56 MHz, and a power of 50 W, and a plasma was formed.
- the mixture was allowed to react for 10 minutes to form a film having a thickness of 0.2 m. Formed.
- the obtained film was uniform and excellent in flatness, and as a result of measurement by an infrared absorption spectrum, it was found that the film was a silicon oxide film and no organic components such as ethoxy groups and ethyl groups remained.
- the film was a silicon oxide film and no organic components such as ethoxy groups and ethyl groups remained.
- a cylindrical quartz reactor having an aluminum plate electrode (2 00mm X 100mmH) and the upper electrode (10
- Omm ⁇ Omm ⁇
- the lower electrode 100 mm ⁇
- the distance between the electrodes was 10 mm.
- a silicon substrate (3 inches ⁇ ) was placed on a susceptor in the reactor, and the substrate was heated and maintained at 250 ° C.
- Hexethoxydisilane heated to 80 ° C. was bubbled with helium at a flow rate of 100 mlZmin (corresponding to 0.27 mlZmin as hexethoxydisilane) and 2,000 ml of helium.
- the pressure inside the reactor was set to 800 mmHg, a glow discharge was generated at a high frequency of 13.56 MHz, and a power of 50 W, the plasma was formed, and the mixture was reacted for 1 minute to form a 0.02 m-thick film. did.
- the obtained film was uniform and excellent in flatness, and as a result of measurement with an infrared absorption spectrum, it was found that the film was a silicon oxide film and no organic components such as ethoxy groups and ethyl groups remained.
- the film was a silicon oxide film and no organic components such as ethoxy groups and ethyl groups remained.
- Example 4 The same procedure as in Example 4 was carried out except that the raw material gas was monosilane, and monosilane lOmlZmin was introduced into the apparatus together with helium 2000 mlZmin and oxygen lOOmlZmin.As a result, generation of fine particles was observed in the reactor, and Had a slight, rough and undulating surface, though partially.
- Example 5 Using the reactor used in Example 5, a polyethylene terephthalate film (50 mm square) was placed on a susceptor and heated and maintained at 70 ° C.
- the raw material was prepared in the same manner as in Example 5, except that hexane ethoxydisilane heated to 80 ° C was bubbled with helium at a flow rate of lOOmlZmin (corresponding to 0.27mlZmin as hexethoxydisilane). Gas, helium and oxygen were introduced into the device.
- the obtained film was uniform and excellent in flatness, and as a result of measurement by an infrared absorption spectrum, it was found that the film was a silicon oxide film and no organic components such as ethoxy groups and ethyl groups remained. It was.
- Example 5 The procedure was as in Example 5, except that monosilane was used as the source gas and monosilane lOmlZmin was introduced into the apparatus together with helium 2000 mlZmin and oxygen lOOmlZmin. It was a powerful force.
- a cylindrical quartz reactor (30 mm ⁇ X 600 mmH) was used as a reactor.
- a silicon substrate (10 mm ⁇ 10 mm) was placed on a susceptor in the reactor, and the substrate was heated and maintained at 400 ° C.
- Hexethoxydisilane heated to 70 ° C was bubbled with nitrogen at a flow rate of 50 mlZmin, and introduced into the above device together with 3000 mlZmin of oxygen.
- the pressure in the reactor was set to 760 mmHg, and the reaction was performed for 240 minutes to form a film having a thickness of 0.12 ⁇ m.
- FIG. 1 shows the infrared absorption spectrum of the obtained film.
- a cylindrical quartz reactor (30 mm ⁇ X 600 mmH) was used as a reaction apparatus.
- a silicon substrate (10 mm ⁇ 10 mm) was placed on a susceptor in the reactor, and the substrate was heated and maintained at 500 ° C.
- Hexethoxydisilane heated to 70 ° C was bubbled with nitrogen at a flow rate of 50 mlZmin, and introduced into the above apparatus together with oxygen at 3000 mlZmin.
- the pressure in the reactor was set to 760 mmHg, and the reaction was performed for 240 minutes to form a 0.15 m-thick film.
- the present invention is effective for manufacturing a highly integrated semiconductor device in which performance is deteriorated when wirings and elements are exposed to high temperatures.
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KR1020067018915A KR101157683B1 (ko) | 2004-02-17 | 2005-02-17 | 실리콘 산화막의 제조 방법 |
JP2005518049A JP4678304B2 (ja) | 2004-02-17 | 2005-02-17 | シリコン酸化膜の製造方法 |
US10/589,077 US7488693B2 (en) | 2004-02-17 | 2005-02-17 | Method for producing silicon oxide film |
EP05719227A EP1717848A4 (en) | 2004-02-17 | 2005-02-17 | PROCESS FOR PRODUCING SILICONE OXIDE FILM |
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- 2005-02-17 KR KR1020067018915A patent/KR101157683B1/ko not_active IP Right Cessation
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US8889566B2 (en) | 2012-09-11 | 2014-11-18 | Applied Materials, Inc. | Low cost flowable dielectric films |
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JP2019104723A (ja) * | 2017-12-08 | 2019-06-27 | ダウ シリコーンズ コーポレーション | ヒドロカルビルオキシジシラン |
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JP4678304B2 (ja) | 2011-04-27 |
KR101157683B1 (ko) | 2012-07-06 |
JPWO2005078784A1 (ja) | 2008-01-17 |
EP1717848A4 (en) | 2010-03-24 |
EP1717848A1 (en) | 2006-11-02 |
US7488693B2 (en) | 2009-02-10 |
US20070173072A1 (en) | 2007-07-26 |
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