JP5329218B2 - シリコン酸化物含有膜の形成方法 - Google Patents
シリコン酸化物含有膜の形成方法 Download PDFInfo
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- JP5329218B2 JP5329218B2 JP2008501327A JP2008501327A JP5329218B2 JP 5329218 B2 JP5329218 B2 JP 5329218B2 JP 2008501327 A JP2008501327 A JP 2008501327A JP 2008501327 A JP2008501327 A JP 2008501327A JP 5329218 B2 JP5329218 B2 JP 5329218B2
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- 238000000034 method Methods 0.000 title claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 38
- 229910052814 silicon oxide Inorganic materials 0.000 title claims description 36
- 239000007789 gas Substances 0.000 claims description 97
- 229910052760 oxygen Inorganic materials 0.000 claims description 73
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 71
- 239000001301 oxygen Substances 0.000 claims description 71
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 238000010926 purge Methods 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 40
- 239000000758 substrate Substances 0.000 claims description 36
- 239000011261 inert gas Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- 238000000231 atomic layer deposition Methods 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000002210 silicon-based material Substances 0.000 claims description 6
- OWKFQWAGPHVFRF-UHFFFAOYSA-N n-(diethylaminosilyl)-n-ethylethanamine Chemical compound CCN(CC)[SiH2]N(CC)CC OWKFQWAGPHVFRF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 238000002513 implantation Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 description 82
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 58
- 229910001873 dinitrogen Inorganic materials 0.000 description 34
- 238000000151 deposition Methods 0.000 description 23
- 230000008021 deposition Effects 0.000 description 23
- 235000012431 wafers Nutrition 0.000 description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 229910000077 silane Inorganic materials 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 150000003377 silicon compounds Chemical class 0.000 description 12
- 238000011144 upstream manufacturing Methods 0.000 description 12
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- VOSJXMPCFODQAR-UHFFFAOYSA-N ac1l3fa4 Chemical compound [SiH3]N([SiH3])[SiH3] VOSJXMPCFODQAR-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- -1 between 4 Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 101100023111 Schizosaccharomyces pombe (strain 972 / ATCC 24843) mfc1 gene Proteins 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 3
- BTHCBXJLLCHNMS-UHFFFAOYSA-N acetyloxysilicon Chemical compound CC(=O)O[Si] BTHCBXJLLCHNMS-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-UHFFFAOYSA-N 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- OOXOBWDOWJBZHX-UHFFFAOYSA-N n-(dimethylaminosilyl)-n-methylmethanamine Chemical compound CN(C)[SiH2]N(C)C OOXOBWDOWJBZHX-UHFFFAOYSA-N 0.000 description 2
- NCAKWMZPHTZJOT-UHFFFAOYSA-N n-[bis(diethylamino)silyl]-n-ethylethanamine Chemical compound CCN(CC)[SiH](N(CC)CC)N(CC)CC NCAKWMZPHTZJOT-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- VEDJZFSRVVQBIL-UHFFFAOYSA-N trisilane Chemical compound [SiH3][SiH2][SiH3] VEDJZFSRVVQBIL-UHFFFAOYSA-N 0.000 description 2
- NSYDOBYFTHLPFM-UHFFFAOYSA-N 2-(2,2-dimethyl-1,3,6,2-dioxazasilocan-6-yl)ethanol Chemical compound C[Si]1(C)OCCN(CCO)CCO1 NSYDOBYFTHLPFM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101000915175 Nicotiana tabacum 5-epi-aristolochene synthase Proteins 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- VEZYCISMGXNHOV-UHFFFAOYSA-N [dimethyl-[(trimethylsilylamino)silylamino]silyl]methane Chemical compound C[Si](C)(C)N[SiH2]N[Si](C)(C)C VEZYCISMGXNHOV-UHFFFAOYSA-N 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- JWJYZMSZUGCIHO-UHFFFAOYSA-N n-[tris(ethylamino)silyl]ethanamine Chemical compound CCN[Si](NCC)(NCC)NCC JWJYZMSZUGCIHO-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- FOQJQXVUMYLJSU-UHFFFAOYSA-N triethoxy(1-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)[Si](OCC)(OCC)OCC FOQJQXVUMYLJSU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- 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
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- C23C16/40—Oxides
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- C23C16/402—Silicon dioxide
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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- 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
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Description
a)反応チャンバ内に基板を収納すること;
b)−式(R1R2N)xSiH4-x、ここでR1およびR2は、H,C1〜C4直線、分岐または環状の炭素鎖で、かつxは1と4の間を含む、を有するアミノシラン、
−式;
Si(OR1)(OR2)(OR3)(OR4),または
(OR1)(OR2)(OR3)SiSi(OR4)(OR5)(OR6)、または
(OR1)(OR2)(OR3)SiRSi(OR4)(OR5)(OR6)、または
Si(O−C(=O)−R1)(O−C(=O)−R2)(O−C(=O)−R3)(O−C(=O)−R4)、好ましくはテトラ(アセトキシ)シランSi(O−C(=O)−Me)4
ここで、R,R1,R2,R3,R4,R5,R6は単独でH,O,C1〜C6直線、
分岐または環状の炭素鎖である、
を有するアルコキシシランまたはアセトキシシラン、
−式(SiH3)nR、nは1と4の間を含み、RはH,N,O,CH2,CH2−
CH2.SiH2,SiH,Siである、を有するシラン、
−式Si(NCO)4を有するテトラ(イソシアネート)シラン
からなる群から選ばれる少なくとも1つのシリコン含有化合物を前記反応チャンバに注入すること、
c)少なくとも1つの酸素含有ガス、好ましくはオゾン、酸素および/または湿気(水分)からなる群から選ばれる、を前記反応チャンバに注入すること、
d)前記基板上に堆積されたシリコン酸化物含有膜を得るために前記反応チャンバ内で少なくとも1つのシリコン含有化合物と少なくとも1つのオゾン含有ガスを500℃未満の温度で反応させること、
e)所期の膜厚が得られるまで工程b)〜d)を繰返すこと、
の工程を含むシリコン酸化物含有膜の形成方法を提供する。
別の実施形態によれば、オゾン含有ガスは、O3/O2比30体積%未満、好ましくは5〜20体積%を持つ酸素とオゾンを含むガス混合物である。
(TSA)トリシリルアミン (SiH3)3N
DSO ジシロキサン (SiH3)2O
BDEAS ビス(ジエチルアミノ)シラン SiH2(NEt2)2
BDMAS ビス(ジメチルアミノ)シラン SiH2(NMe2)2
TriDMAS トリス(ジエチルアミノ)シラン SiH(NMe2)3
ビス(トリメチルシリルアミノ)シラン SiH2(NHSiMe3)2
TICS テトラ(イソシアネート)シラン Si(NCO)4
TEAS テトラキス(エチルアミノ)シラン Si(NHEt)4
TEOS テトラキス(エトキシ)シラン Si(OEt)4
BTESE ビス(トリエトキシシリル)エタン (EtO)3Si−CH2−CH2−Si(OEt)3
TAS テトラ(アセトキシ)シラン Si(−O−C(=O)−Me)4
からなる群から好ましくは選ばれるべきである。
−酸素源と式(R1R2N)xSiH4-x、ここでR1およびR2は、別個にH,C1〜C 6 直線、分岐または環状の炭素鎖で、かつxは1と4の間を含む、を有するアミノシランとの使用は、独立して反応器に連続的またはパルスによって導入される。好ましくは、ALD方法を通して注入される。
(OR1)(OR2)(OR3)SiSi(OR4)(OR5)(OR6)、または
(OR1)(OR2)(OR3)SiRSi(OR4)(OR5)(OR6)、または
Si(O−C(=O)−R1)(O−C(=O)−R2)(O−C(=O)−R3)(O−C(=O)−R4)、好ましくはテトラ(アセトキシ)シランSi(O−C(=O)−Me)4
ここで、R,R1,R2,R3,R4,R5,R6は別個にH,O,C1〜C6直線、分岐または環状の炭素鎖である、を有するアルコキシシランまたはアセトキシシランとは独立して反応器に連続的またはパルスによって導入される。好ましくは、ALD方法を通して注入される。好ましいアルコキシシランは、(EtO)3Si−CH2−CH2−Si(OEt)3(BTESE)である。アルキルアミノシランは、基板表面に吸着される(初期段階で、この工程が酸素源の導入の間に、下地金属電極の起こりえる酸化を妨げる)。不活性ガスを用いて反応器からアミノシランを排気するためのパージ時間の後に、酸素/オゾンガス混合物(典型的に:酸素中の5〜20体積%のオゾン)、酸素、水分および/または過酸化水素(H2O2)またはこれらの組合せからなる酸素源はパルスで導入される。サイクルは、それからアルコキシシランの1パルス、パージガスの1パルス、酸素含有ガスの1パルス、パージガスの1パルスからなる。サイクル数は、所望の経験条件で得られるサイクル当たりの堆積速度を考慮に入れて目標厚さによって決定される。堆積温度は、0.1〜100Torr(13〜13300Pa)の操作圧力で室温と同じ位低くかつ500℃までできる。非常に低酸素かつ低水素量の高品質膜は、0.1〜100Torr(13〜13300Pa)間の圧力で200〜400℃の間で堆積されることが好ましい。
処理基板、例えば半導体ウェハ(図示せず)は反応チャンバ11内のサセプタ上に載置され、ウェハはそのサセプタに内蔵された温度調節器によりを50〜400℃の温度に加熱される。図1に示すように開閉弁V5、V7を閉じ、これ以外の開閉弁V1〜V4、V6、V5’、V7’を全て開く。図1において、閉じた制御弁は黒で塗りつぶし、開放された制御弁を白抜きとして表示する。また、以下の説明における開閉弁の開閉状態も同様に表示する。
図1に示す状態からの進行において、図2に示すように分岐ラインL4’の開閉弁V5’が閉じられ、この動作に同期して、ラインL4の開閉弁V5が開く。所望時間後にこれらの各開閉弁V5、V5’の状態が反転される。開閉弁V5の開の期間に、Si化合物ガスシリンダ13からSi化合物ガスが流量制御の下でラインL4からラインL1に供給され、窒素ガスと一緒に反応チャンバ11内にパルスされる。このパルスは、反応チャンバ11内のサセプタに載置された半導体ウェハの加熱された表面にSi化合物の近似した単分子層の吸着をもたらす。
前記Si化合物ガスパルスが導入された後に、窒素ガスパージはラインL4および分岐ラインL4’の開閉弁V5、V5’の状態を図2に示す状態から反転させることによって、図1として遂行される。このとき、反応チャンバ11内に残留した未反応のSi化合物が窒素ガスにより排出され、反応チャンバ11の内部が窒素ガスで再び置換される。
図1に示す状態からからの進行において、図3に示すように分岐ラインL6’の開閉弁V7’が閉じられ、この動作に同期して、ラインL6の開閉弁V7を開かれる。所望時間後に開閉弁V7、V7’の状態が反転される。開閉弁V7が開かれる期間に、オゾンと酸素の混合ガスはラインL6からラインL1に供給され、窒素ガスと一緒に反応チャンバ11内にパルスされる。このパルスの結果、反応チャンバ11内のサセプタに載置された半導体ウェハの加熱された表面に吸着されたSi化合物はオゾン+酸素の混合ガスで酸化され、近似した単分子層の形態で半導体ウェハ表面のシリコン酸化物膜の形成をもたらす。
前述した図1〜図3に示す膜形成装置を用いた。シリコンウェハは、反応チャンバ11内のサセプタに設置し、ウェハは100℃に加熱した。シリコン酸化物膜は、以下に述べる条件を用いる前述した実施形態に従って1)窒素ガスパージ、2)Si化合物ガスパルス、3)窒素ガスパージおよび4)オゾン+酸素の混合ガスのパルスの工程を繰り返して形成した。
・反応チャンバ内圧力:3Torr、
・窒素ガス供給流量:130sccm、
・窒素ガスパージ時間:6秒間。
・反応チャンバ内圧力:3Torr、
・Si化合物ガス:トリシリルアミン(TSA)ガス、
・TSAガス供給流量:2sccm、
・TSAパルス時間:1秒間。
・反応チャンバ内圧力:3Torr、
・窒素ガス供給流量:130sccm、
・窒素ガスパージ時間:6秒間。
・反応チャンバ内圧力:3Torr、
・オゾン+酸素混合ガス(5%オゾン濃度)の供給流量:20sccm、
・混合ガスパルス時間:2秒間。
シリコン酸化物膜は例1と同様な方法によりを形成したが、この場合、反応チャンバ11内のサセプタに設置したシリコンウェハを200℃に加熱した。
シリコン酸化物膜は例1と同様な方法によりを形成したが、この場合、反応チャンバ11内のサセプタに設置したシリコンウェハを300℃に加熱した。
BDEASおよびオゾンを用いるSiO2膜のALD堆積
膜は、図1〜図3の構成を用い、BDEASとオゾン/酸素の混合物を用いるALDによってシリコンおよびイリジウム上に順調に堆積した。
− 7.0sccm O3
− 93sccm O2
− BDEAS:1sccm[1〜7sccmの範囲内]
− N2:50sccm
− 200と400℃の間の温度範囲
− 操作圧力:1Torr[0.1〜5Torrの範囲内]
− パージおよびパルス時間は典型的にそれぞれ5秒間に設定した、
− サイクル数は典型的に600サイクルに設定した、
であった。
BDMASおよびオゾンを用いるSiO2膜のALD堆積
同様な実験は、例4と同様な条件で遂行した。高品質膜は、1Torr,250〜300℃の間で0.3Å/サイクルの堆積速度で得た。
TriDMASおよびオゾンを用いるSiO2膜のALD堆積
同様な実験は、例4と同様な条件で遂行した。高品質膜は、1Torr,250〜300℃の間で0.2Å/サイクルの堆積速度で得た。
TSA,オゾンおよび触媒[Hf(NEt2)4]を用いるSiO2膜のALD堆積
膜は、窒素で希釈されるHf(NEt2)4、N,TSA,Nとオゾン/酸素O3/O2混合物(Hf(NEt2)4にマスフローコントローラを通してバブリングする窒素は反応器11に同様な方法で択一的に供給されるこの触媒とN2の混合物に供する)を択一的に導入するALDによってシリコン上に順調に堆積した。
− 4sccm O3
− 96sccm O2
− TSA:1sccm[1〜7sccmの範囲内]
− N2:100sccm
− 温度:400℃
− 操作圧力:5Torr
− パルス期間は典型的にそれぞれ5秒間に設定したかつパルス期間10秒間、
− サイクル数は44サイクルであった、
であった。
Claims (15)
- a)反応チャンバ内に基板を収納すること;
b)−BDEAS ビス(ジエチルアミノ)シランSiH2(NEt2)2の少なくとも1つのシリコン含有化合物を前記反応チャンバに注入すること、
c)酸素に対するオゾン比が20体積%未満の酸素およびオゾンを含む少なくとも1つのガス混合物を前記反応チャンバに注入すること、
d)前記基板上に堆積されたシリコン酸化物含有膜を得るために前記反応チャンバ内で少なくとも1つのシリコン含有化合物と少なくとも1つのガス混合物を400℃未満の温度で反応させること、
e)所期の膜厚が得られるまで工程b)〜d)を繰返すこと、
の工程を含むシリコン酸化物含有膜の形成方法。 - 前記基板は、その導入後、工程b)、c)、d)およびまたはe)をなす前に反応チャンバ内で加熱される請求項1記載の方法。
- 少なくとも1つの工程b)および/またはc)は、少なくとも1つの前記化合物および/またはガス混合物の中断された注入によってなされる請求項1または2記載の方法。
- パルス化学気相堆積(CVD)または原子層堆積(ALD)は、前記反応チャンバ内でなされる請求項1〜3いずれか記載の方法。
- 少なくとも1つの化合物および少なくとも1つのガス混合物の同時注入は、前記反応チャンバ内でなされる請求項1〜4いずれか記載の方法。
- 少なくとも1つの化合物および少なくとも1つのガス混合物の択一的な注入は、前記反応チャンバ内でなされる請求項1〜4いずれか記載の方法。
- 少なくとも1つの化合物または少なくとも1つのガス混合物は、別の化合物および/または少なくとも1つのガス混合物の注入前に前記基板表面に吸着される請求項1〜6いずれか記載の方法。
- 各化合物および/またはガス混合物注入は、前記反応チャンバ内へのパージガス注入の後に続く請求項1〜7いずれか記載の方法。
- 化合物および/またはガス混合物注入は、所期のSiO2含有膜厚が得られるまで繰返される請求項1〜8いずれか記載の方法。
- 前記反応チャンバ圧力は、最大100Torrである請求項1〜9いずれか記載の方法。
- 前記SiO2含有膜中のH結合量は、8×1021原子/cc未満である請求項1〜10いずれか記載の方法。
- 前記ガス混合物は、酸素に対するオゾン比が5〜20体積%である請求項1〜11いずれか記載の方法。
- 前記ガス混合物は、不活性ガスで希釈される請求項12記載の方法。
- 不活性ガスもまた前記反応チャンバ内に導入される請求項1〜13いずれか記載の方法。
- 1%より少量のHf(NEt2)4またはNHEt2の触媒は、前記反応チャンバ内に導入される請求項1〜14いずれか記載の方法。
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KR101248358B1 (ko) | 2013-04-03 |
WO2006097525A2 (en) | 2006-09-21 |
TW200707582A (en) | 2007-02-16 |
US20120276292A1 (en) | 2012-11-01 |
JP5631958B2 (ja) | 2014-11-26 |
KR20140069192A (ko) | 2014-06-09 |
KR100961805B1 (ko) | 2010-06-08 |
JP2013070077A (ja) | 2013-04-18 |
JP2006261434A (ja) | 2006-09-28 |
KR20150047631A (ko) | 2015-05-04 |
TW201403715A (zh) | 2014-01-16 |
EP1861519B1 (en) | 2010-09-22 |
US20090232985A1 (en) | 2009-09-17 |
WO2006097525A3 (en) | 2006-11-23 |
TWI515794B (zh) | 2016-01-01 |
KR20120044992A (ko) | 2012-05-08 |
ATE482301T1 (de) | 2010-10-15 |
JP2008533731A (ja) | 2008-08-21 |
KR20070114393A (ko) | 2007-12-03 |
KR20130027573A (ko) | 2013-03-15 |
DE602006017042D1 (de) | 2010-11-04 |
EP1861519A2 (en) | 2007-12-05 |
KR20090107090A (ko) | 2009-10-12 |
CN101171366A (zh) | 2008-04-30 |
US8613976B2 (en) | 2013-12-24 |
TWI435387B (zh) | 2014-04-21 |
US8227032B2 (en) | 2012-07-24 |
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