CN109154080B - 薄膜形成用原料及薄膜的制造方法 - Google Patents
薄膜形成用原料及薄膜的制造方法 Download PDFInfo
- Publication number
- CN109154080B CN109154080B CN201780031611.4A CN201780031611A CN109154080B CN 109154080 B CN109154080 B CN 109154080B CN 201780031611 A CN201780031611 A CN 201780031611A CN 109154080 B CN109154080 B CN 109154080B
- Authority
- CN
- China
- Prior art keywords
- thin film
- raw material
- group
- forming
- film forming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 150
- 239000002994 raw material Substances 0.000 title claims description 74
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052735 hafnium Chemical group 0.000 claims abstract description 15
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 68
- -1 propane-1, 2-diyl group Chemical group 0.000 claims description 40
- 239000010408 film Substances 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 33
- 230000008016 vaporization Effects 0.000 claims description 16
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 239000002243 precursor Substances 0.000 description 35
- 239000007789 gas Substances 0.000 description 30
- 238000005229 chemical vapour deposition Methods 0.000 description 27
- 238000000231 atomic layer deposition Methods 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000000151 deposition Methods 0.000 description 19
- 230000008021 deposition Effects 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910044991 metal oxide Inorganic materials 0.000 description 12
- 150000004706 metal oxides Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000005755 formation reaction Methods 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000009834 vaporization Methods 0.000 description 9
- 229910000449 hafnium oxide Inorganic materials 0.000 description 8
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 8
- 239000012434 nucleophilic reagent Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 238000003852 thin film production method Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- 125000004663 dialkyl amino group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- OOFGXDQWDNJDIS-UHFFFAOYSA-N oxathiolane Chemical compound C1COSC1 OOFGXDQWDNJDIS-UHFFFAOYSA-N 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000002910 rare earth metals Chemical group 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- BGYBONWLWSMGNV-UHFFFAOYSA-N 1,4,7,10,13,16,19,22-octaoxacyclotetracosane Chemical compound C1COCCOCCOCCOCCOCCOCCOCCO1 BGYBONWLWSMGNV-UHFFFAOYSA-N 0.000 description 1
- QBPPRVHXOZRESW-UHFFFAOYSA-N 1,4,7,10-tetraazacyclododecane Chemical compound C1CNCCNCCNCCN1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 description 1
- MDAXKAUIABOHTD-UHFFFAOYSA-N 1,4,8,11-tetraazacyclotetradecane Chemical compound C1CNCCNCCCNCCNC1 MDAXKAUIABOHTD-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- PLHCSZRZWOWUBW-UHFFFAOYSA-N 2-methoxyethyl 3-oxobutanoate Chemical compound COCCOC(=O)CC(C)=O PLHCSZRZWOWUBW-UHFFFAOYSA-N 0.000 description 1
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- MGWYSXZGBRHJNE-UHFFFAOYSA-N cyclohexane-1,4-dicarbonitrile Chemical compound N#CC1CCC(C#N)CC1 MGWYSXZGBRHJNE-UHFFFAOYSA-N 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 125000004984 dialkylaminoalkoxy group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- QMLGNDFKJAFKGZ-UHFFFAOYSA-N dicyclohexano-24-crown-8 Chemical compound O1CCOCCOCCOC2CCCCC2OCCOCCOCCOC2CCCCC21 QMLGNDFKJAFKGZ-UHFFFAOYSA-N 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 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
- RQFCJASXJCIDSX-UUOKFMHZSA-N guanosine 5'-monophosphate Chemical compound C1=2NC(N)=NC(=O)C=2N=CN1[C@@H]1O[C@H](COP(O)(O)=O)[C@@H](O)[C@H]1O RQFCJASXJCIDSX-UUOKFMHZSA-N 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 1
- ILPNRWUGFSPGAA-UHFFFAOYSA-N heptane-2,4-dione Chemical compound CCCC(=O)CC(C)=O ILPNRWUGFSPGAA-UHFFFAOYSA-N 0.000 description 1
- DGCTVLNZTFDPDJ-UHFFFAOYSA-N heptane-3,5-dione Chemical compound CCC(=O)CC(=O)CC DGCTVLNZTFDPDJ-UHFFFAOYSA-N 0.000 description 1
- SDAXRHHPNYTELL-UHFFFAOYSA-N heptanenitrile Chemical compound CCCCCCC#N SDAXRHHPNYTELL-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical compound NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 125000005353 silylalkyl group Chemical group 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 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
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- 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
- C23C16/06—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 metallic material
- C23C16/18—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 metallic material from metallo-organic compounds
-
- 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
-
- 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
- C23C16/405—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- 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
- H01L21/02172—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02181—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
-
- 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
- H01L21/02172—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02186—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing titanium, e.g. TiO2
-
- 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
- H01L21/02172—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02189—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 at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing zirconium, e.g. ZrO2
-
- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
【技术领域】
本发明涉及一种含有特定的化合物而成的薄膜形成用原料及使用 该薄膜形成用原料的薄膜的制造方法。
【背景技术】
含有钛、锆或铪的薄膜材料被应用于半导体、太阳能电池 (photovoltaic cell)、TFT等的用途,其中主要使用作为半导体材 料用的高介电材料。
作为上述薄膜的制造法,可举例为溅镀法、离子镀敷法、涂布热 分解法或溶凝胶法等的MOD法、化学气相成长法等,但包含ALD (Atomic Layer Deposition)法的化学气相成长法(以下有时也简单 地记载为CVD)法,由于具有组成控制性、逐步包覆性优异,适于量产 化,且可以混合累积(hybrid accumulation)等的多种优点,故为最 适的制造过程。
作为化学气相成长法所使用的金属供给源,多数报告有各种原料。
例如在专利文献1中,公开了作为可使用于CVD法或ALD法的材 料而使用特定的锆配合物。另外,在专利文献2中,公开了作为可使 用于CVD法或ALD法的材料而使用特定的金属配合物。在专利文献1 及专利文献2中,未具体记载本发明的薄膜形成用原料。
[现有技术文献]
[专利文献]
[专利文献1]韩国专利10-1263454号
[专利文献2]韩国公开10-2014-0078534号
【发明内容】
[发明要解决的课题]
使化学气相成长用原料等气化而在基材表面形成含有金属的薄膜 时,为得到高品质的薄膜而必须在高温下进行成膜,故要求热稳定性 高的薄膜形成用原料。另外,可要求于宽高比(aspect ratio)为10~ 200左右的沟中可均匀地形成薄膜的薄膜形成用原料。
[用以解决课题的手段]
本发明人等重复讨论的结果,发现含有特定的化合物的薄膜形成 用原料可解决上述课题,因而完成本发明。
本发明提供一种薄膜形成用原料,其含有以下述通式(1)表示的 化合物而成:
[化1]
(式中,R1是表示碳原子数2~4的直链或分支状的烷基,R2~R5各自独立表示碳原子数1~4的直链或分支状的烷基,A是表示碳原子 数1~4的烷二基,M是表示钛、锆或铪。但,M为锆时,A是碳原子 数3或4的烷二基)。
另外,本发明提供一种薄膜的制造方法,其将含有使上述薄膜形 成用原料气化而得到的通式(1)表示的化合物的蒸气,导入设置有基 体的成膜腔室内,使该化合物分解及/或使其进行化学反应而在该基体 的表面形成含有选自钛、锆及铪中至少1种的原子的薄膜。
[发明的效果]
依据本发明,可获得热稳定性高,于宽高比为10~200左右的沟 中可均匀地形成高品质的薄膜的薄膜形成用原料。本发明的薄膜形成 用原料适合作为利用CVD法的金属薄膜形成用的原料。本发明的薄膜 形成用原料可适用于ALD法,故特别适合作为达到上述效果的ALD法 用薄膜形成用原料。
【附图的简单说明】
[图1]图1为表示本发明的薄膜的制造方法中可使用的化学气相 成长用装置的一例的概要图。
[图2]图2为表示本发明的薄膜的制造方法中可使用的化学气相 成长用装置的另一例的概要图。
[图3]图3为表示本发明的薄膜的制造方法中可使用的化学气相 成长用装置的一例的概要图。
[图4]图4为表示本发明的薄膜的制造方法中可使用的化学气相 成长用装置的一例的概要图。
【具体实施方式】
本发明的薄膜形成用原料含有以上述通式(1)表示的化合物,且合 适地作为具有CVD法等的气化步骤的薄膜制造方法的前体,也可使用 ALD法形成薄膜。
上述通式(1)中,R1是表示碳原子数2~4的直链或分支状的烷基, R2~R5各自独立表示碳原子数1~4的直链或分支状的烷基,A是表示 碳原子数1~4的烷二基,M是表示钛、锆或铪;但,M为锆时,A是 碳原子数3或4的烷二基。
作为以上述R1表示的碳原子数2~4的直链或分支状的烷基可举 例乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基等。另外, 作为上述R2~R5表示的碳原子数1~4的直链或分支状的烷基可举例甲 基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基等。
作为以上述A表示的碳原子数1~4的烷二基可举例亚甲基、亚乙 基、丙烷-1,3-二基、丙烷-1,2-二基、丁烷-1,4-二基、丁烷-1,3-二 基等。作为以上述A表示的碳原子数3或4的烷二基可举例丙烷-1,3- 二基、丙烷-1,2-二基、丁烷-1,4-二基、丁烷-1,3-二基等。
上述通式(1)中,M为钛及铪时,A为碳原子数2或3的烷二基时, 热稳定性高,使用ALD法成膜时,可对基体上的宽高比高的沟的部分 均匀形成薄膜,故是优选的,其中,为碳原子数3的烷二基时,使用 ALD法成膜时,对基体上的宽高比高的沟的部分均匀地形成薄膜的效 果高,故是优选的。M为锆时,A为碳原子数3的烷二基时,使用ALD 法成膜时,对基体上的宽高比高的沟的部分均匀地形成薄膜的效果高, 故是优选的。上述通式(1)中,R1为乙基、异丙基、仲丁基及叔丁基 的任一者时,使用ALD法成膜时,可对基体上的宽高比高的沟的部分 均匀地形成薄膜,故是优选的。R2~R5之中1个以上为甲基时,蒸气 压高,故是优选的。其中,R2及R4为甲基且R3及R5为乙基时,熔点低、 输送性良好,故是优选的。利用并未伴随气化步骤的MOD法的薄膜的 制造方法时,R1~R5及A可对于所使用的溶剂的溶解性、薄膜形成反 应等适当选择。
作为以通式(1)表示的化合物的优选具体例可举例下述化学式 No.1~No.88表示的化合物。需要说明的是,下述化学式No.1~No.88 中,“Me”表示甲基,“Et”表示乙基,“iPr”表示异丙基,“sBu” 表示仲丁基,“tBu”表示叔丁基。
[化3]
[化4]
[化5]
[化6]
[化7]
以本发明的薄膜形成用原料所含有的通式(1)所表示的化合物依 据其制造方法但并无特别地限制,可应用周知的反应而制造。例如,M 为钛时,在甲苯等的溶剂中的四(二烷基氨基)钛中,使对应的构造 的烷基胺烷基环戊二烯化合物在10~50℃的温度条件下反应即可。M 为锆时,在甲苯等的溶剂中,使对应的构造的烷基胺烷基环戊二烯化 合物于四(二烷基氨基)锆中,在10~50℃的温度条件下反应即可。 M为铪时,在甲苯等的溶剂中,使对应的构造的烷基胺烷基环戊二烯 化合物于四(二烷基氨基)铪中,在10~50℃的温度条件下反应即可。
本发明的薄膜形成用原料的形态可依据适用该薄膜形成用原料的 制造过程而相异。例如,制造仅包含选自钛、锆及铪所成的群中金属 的薄膜时,本发明的薄膜形成用原料不含有以通式(1)表示的化合物 以外的金属化合物及半金属化合物。另一方面,制造包含选自钛、锆 及铪所成的群中选出的金属与选自钛、锆及铪所成的群中选出的金属 以外的金属及/半金属的薄膜时,本发明的薄膜形成用原料,含有包含 选自钛、锆及铪所成的群中选出的金属以外的金属及/半金属的的化合 物(以下也称为“其他前体”)。本发明的薄膜形成用原料如后述, 也可进而含有有机溶剂及/亲核性试药。本发明的薄膜形成用原料如上述说明,由于适用于CVD法、ALD法,故特别作为化学气相成长用原 料(以下有时也称为“CVD用原料”)有用。
本发明的薄膜形成用原料为化学气相成长用原料时,其形态可根 据所使用的CVD法的输送供给方法等方法而适当选择。
作为上述的输送供给方法,有将CVD用原料于储存该原料的容器 (以下有时也简单记载为原料容器)中加热及/减压而气化为蒸气,将 该蒸气与根据需要使用的氩、氮、氦等的载气一起导入设置基体的成 膜腔室内(以下有时也记载为堆积反应部)的气体输送法,将CVD用原 料以液体或溶液状态输送至气化室,在气化室通过加热及/减压而气化 为蒸气,将该蒸气导入成膜腔室内的液体输送法。气体输送法时,以 上述通式(1)表示的化合物本身可使用作为CVD用原料。液体输送法 时,可将以上述通式(1)表示的化合物本身或该化合物溶于有机溶剂 中的溶液作为CVD用原料。另外,这些CVD用原料也可进而包含其他前体或亲核性试药等。
另外,在多成分体系的CVD法中,有使CVD用原料各成分独立气 化并供给的方法(以下有时也记载为单一源法)与使多成分原料预先 以期望组成混合的混合原料气化并供给的方法(以下有时也记载为混 合源法)。混合源法时,可将本发明的薄膜形成用原料可以将通式(1) 表示的化合物与其他前体的混合物或将该混合物溶于有机溶剂的混合 溶液作为CVD用原料。该混合物或混合溶液也可进而包含亲核性试药 等。
上述有机溶剂并未特别限制,可使用周知的一般有机溶剂。作为 有机溶剂举例为例如乙酸乙酯、乙酸丁酯、乙酸甲氧基乙酯等的乙酸 酯类;四氢呋喃、四氢吡喃、乙二醇二甲醚、二乙二醇二甲醚、三乙 二醇二甲醚、二丁醚、二烷等醚类;甲基丁基酮、甲基异丁基酮、 乙基丁基酮、二丙基酮、二异丁基酮、甲基戊基酮、环己酮、甲基环 己酮等的酮类;己烷、环己烷、甲基环己烷、二甲基环己烷、乙基环 己烷、庚烷、辛烷、甲苯、二甲苯等的烃类;1-氰基丙烷、1-氰基丁 烷、1-氰基己垸、氰基环己烷、氰基苯、1,3-二氰基丙烷、1,4-二氰基丁烷、1,6-二氰基己烷、1,4-二氰基环己烷、1,4-二氰基苯等的具 有氰基的烃类;吡啶、甲基吡啶等,这些有机溶剂可根据溶质的溶解 性、使用温度与沸点、起火点的关系等而单独使用或混合两种以上使 用。使用这些有机溶剂时,将前体溶解于有机溶剂的溶液的CVD用原 料中的前体全体量为0.01~2.0摩尔/升是优选的,特优选为0.05~ 1.0摩尔/升。所谓前体全体量,于本发明的薄膜形成用原料不含有以 通式(1)表示的化合物以外的金属化合物及半金属化合物时,为以通 式(1)表示的化合物的量,于本发明的薄膜形成用原料中除了以通式 (1)表示的化合物以外又含有包含其他金属的化合物及包含半金属的 化合物(其他前体)时,为以通式(1)表示的化合物及其他前体的合 计量。
而且,在多成分体系的CVD法时,作为与本发明的薄膜形成用原 料一起使用的其他前体并未特别限制,可使用CVD原料中所用的周知 一般前体。
作为其他前体,可举例具有下述作为配位基的化合物所成的群中 选择的1种或2种以上的硅或金属的化合物:氢化物、氢氧化物、卤 化物、叠氮化物、烷基、烯基、环烷基、芳基、炔基、氨基、二烷氨 基烷基、单烷氨基、二烷氨基、二胺、二(硅烷基-烷基)氨基、二(烷基-硅烷基)氨基、二硅烷基氨基、烷氧基、烷氧基烷基、联胺、磷化 物、腈、二烷氨基烷氧基、烷氧基烷基二烷基胺、硅氧基、二酮酸酯 基、环戊二烯基、硅烷基、吡唑酸酯(pyrazolate)、胍酸酯 (guanidinate)、磷胍酸酯、脒酸酯、磷米酸酯、酮亚胺酸酯 (ketoiminate)、二酮亚胺酸酯(diketoiminate)、羰基及磷脒酸 酯(phosphoamidinate)。
作为其他前体的金属种,举例为镁、钙、锶、钡、镭、钪、钇、 钒、铌、钽、铬、钼、钨、锰、铁、锇、钴、铑、铱、镍、钯、铂、 铜、银、金、锌、镉、铝、镓、铟、锗、锡、铅、锑、铋、镧、铈、 镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱。
上述的其他前体为本技术领域中公知的,其制造方法也为公知。 若举制造方法的一例,在例如使用醇化合物作为有机配位基时,通过 使如前述的金属无机盐或其水合物与该醇化合物的碱金属烷氧化物反 应,可制造前体。此处,金属的无机盐或其水合物可举例为金属的卤 化物、硝酸盐等,作为碱金属烷氧化物可举例为烷氧基钠、烷氧基锂、 烷氧基钾等。
上述的其他前体,在单一源法时,优选为热及/氧化分解行为与以 通式(1)表示的化合物类似的化合物,在混合源法时,除了热及/氧化 分解行为类似以外,优选为混合时不引起因化学反应等产生的变质的 物质。
作为上述的其他前体可举例如包含稀土类元素的前体。作为包含 稀土类元素的前体可举例以下述式(III-1)~(III-3)表示的化合物。
[化8]
(式中,M2表示稀土类原子,Ra及Rb各独立地表示可经卤原子取代 的、链中可包含氧原子的碳原子数1~20的烷基,Rc表示碳原子数1~ 8的烷基,Re及Rf各独立地表示氢原子或碳原子数1~3的烷基,Rg及 Rj各独立地表示氢原子或碳原子数1~4的烷基,p’表示0~3的整数, r’表示0~2的整数)。
包含上述的稀土类元素的其他前体中,M2表示的稀土类原子举例 为钪、钇、镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、 镥等。作为以Ra及Rb表示的、可经卤原子取代的、链中可包含氧原子 的碳原子数1~20的烷基可举例甲基、乙基、丙基、异丙基、丁基、 仲丁基、叔丁基、异丁基、戊基、异戊基、新戊基、叔戊基、己基、 环己基、1-甲基环己基、庚基、3-庚基、异庚基、叔庚基、正辛基、 异辛基、叔辛基、2-乙基己基、三氟甲基、全氟己基、2-甲氧基乙基、 2-乙氧基乙基、2-丁氧基乙基、2-(2-甲氧基乙氧基)乙基、1-甲氧基 -1,1-二甲基甲基、2-甲氧基-1,1-二甲基乙基、2-乙氧基-1,1-二甲 基乙基、2-异丙氧基-1,1-二甲基乙基、2-丁氧基-1,1-二甲基乙基、 2-(2-甲氧基乙氧基)-1,1-二甲基乙基等。另外,作为以Rc表示的 碳原子数1~8的烷基可举例甲基、乙基、丙基、异丙基、丁基、仲丁 基、叔丁基、异丁基、戊基、异戊基、新戊基、叔戊基、己基、1-乙 基戊基、环己基、1-甲基环己基、庚基、异庚基、叔庚基、正辛基、 异辛基、叔辛基、2-乙基己基等。另外,作为以Re及Rf表示的碳原子 数1~3的烷基可举例甲基、乙基、丙基、2-丙基等,作为以Rg及Rj表示的碳原子数1~4的烷基可举例甲基、乙基、丙基、异丙基、丁基、 仲丁基、叔丁基、异丁基等。
另外,于本发明的薄膜形成用材料中,根据需要,为了赋予以上 述通式(1)表示的化合物及其他前体的稳定性,也可含有亲核性试药。 作为亲核性试药举例为甘醇二甲醚、二甘醇二甲醚、三甘醇二甲醚、 四甘醇二甲醚等的乙二醇醚类,18-冠状醚-6、二环己基-18-冠状醚-6、 24-冠状醚-8、二环己基-24-冠状醚-8、二苯并-24-冠状醚-8等的冠 状醚类,乙二胺、N,N’-四甲基乙二胺、二亚乙基三胺、三亚乙基四 胺、四亚乙基五胺、五亚乙基六胺、1,1,4,7,7-五甲基二亚乙基三胺、 1,1,4,7,10,10-六甲基三亚乙基四胺、三乙氧基三亚乙基胺等的聚胺 类,四氮杂环十四烷(cyclam)、四氮杂环十二烷(cyclen)等的环状聚胺类、吡啶、吡咯烷、哌啶、吗啉、N-甲基吡咯烷、N-甲基哌啶、 N-甲基吗啉、四氢呋喃、四氢吡喃、1,4-二烷、唑、噻唑、氧硫 杂环戊烷(oxathiolane)等的杂环化合物类、乙酰乙酸甲酯、乙酰乙 酸乙酯、乙酰乙酸-2-甲氧基乙酯等的β-酮酯类或乙酰丙酮、2,4-己 二酮、2,4-庚二酮、3,5-庚二酮、二特戊酰基甲烷(dipivaloyl methane) 等的β-二酮类,这些亲核性试药的使用量,对于前体全体的量1摩尔, 更优选为0.1摩尔~10摩尔的范围,更优选为1~4摩尔。
本发明的薄膜形成用原料极力地不含构成其的成分以外的杂质金 属元素分、杂质氯等的杂质卤素分及杂质有机分。杂质金属元素分的 每种元素100ppb以下是优选的,更优选为10ppb以下,总量计为1ppm 以下是优选的,更优选为100ppb以下。尤其,使用作为LSI的闸极绝 缘膜、闸极膜、障壁层时,必须减少对所得薄膜的电特性有影响的碱 金属元素及碱土类金属元素的含量。而且,杂质卤素分100ppm以下是 优选的,更优选为10ppm以下,最优选为1ppm以下。杂质有机分总量 计为500ppm以下是优选的,更优选为50ppm以下,最优选为10ppm 以下。另外,由于水分是化学气相成长用原料中的颗粒发生或薄膜形 成中的颗粒发生的原因,故金属化合物、有机溶剂及亲核性试药中, 为了减低各自的水分,使用时可以预先尽可能去除水分。金属化合物、 有机溶剂及亲核性试药各自的水分量10ppm以下是优选的,更优选为 1ppm以下。
另外,本发明的薄膜形成用原料,为了减低或防止所形成的薄膜 的颗粒污染,优选极力不含颗粒。具体而言,在液相的通过光散射式 液中粒子检测器的颗粒测定中,大于0.3μm的粒子数在液相1ml中 100个以下是优选的,大于0.2μm的粒子数在液相1ml中更优选为 1000个以下,大于0.2μm的粒子数在液相1ml中最优选为100个以下。
作为使用本发明的薄膜形成用原料制造薄膜的本发明的薄膜的制 造方法,为将本发明的薄膜形成用原料气化的蒸气以及根据需要使用 的反应性气体导入设置基体的成膜腔室内,其次,使前体于基体上分 解及/或化学反应,于基体表面成长并堆积含金属的薄膜的CVD法。原 料的输送供给方法、堆积方法、制造条件、制造装置等并未特别受到 限制,可使用周知的一般条件及方法。
作为上述根据需要使用的反应性气体,例如作为氧化性的物质可 举例氧、臭氧、二氧化氮、一氧化氮、水蒸气、过氧化氢、甲酸、乙 酸、乙酸酐等,作为还原性的物质可举例氢,且作为制造氮化物的物 质,举例为单烷基胺、二烷基胺、三烷基胺、亚烷基二胺等的有机胺 化合物、联胺、氨等,这些可使用1种或2种以上。
而且,作为上述输送供给方法,举例为前述的气体输送法、液体 输送法、单一源法、混合源法等。
另外,作为上述的堆积方法,可举例使原料气体或使原料气体与 反应性气体仅通过热而反应并堆积薄膜的热CVD,使用热及等离子体 (plasma)的等离子体CVD,使用热与光的光CVD,使用热、光及等离 子体的光等离子体CVD,将CVD的堆积反应分为基本过程,以分子等 级进行阶段性堆积的ALD。
作为上述基体的材质可举例硅;氮化硅、氮化钛、氮化钽、氧化 钛、氮化钛、氧化钌、氧化锆、氧化铪、氧化镧等的陶瓷;玻璃;金 属钌等的金属。作为基体的形状可举例板状、球状、纤维状、鳞片状, 基体表面可为平面,也可成为具有宽高比为10~200左右的沟槽(沟) 沟槽构造等的三维构造。
而且,作为上述制造条件,举例为反应温度(基体温度)、反应压 力、堆积速度等。关于反应温度,以通式(1)表示的化合物充分反应 的温度的100℃以上是优选的,更优选为150℃~400℃。以通式(1) 表示的的化合物由于在未达300℃时可热分解,故特优选为150℃~ 250℃。另外,反应压力于热CVD或光CVD时,大气压~10Pa是优选 的,使用等离子体时,优选2000Pa~10Pa。
另外,堆积速度可通过原料的供给条件(气化温度、气化压力)、 反应温度、反应压力而控制。堆积速度若大,则有所得薄膜特性恶化 的情况,若小时,有产生生产性问题时,因此0.01~100nm/分钟是优 选的,更优选为1~50nm/分钟。而且,ALD法时,以循环次数进行控 制以获得所期望膜厚。
作为上述制造条件进而举例为使薄膜形成用原料气化成为蒸气时 的温度或压力。使薄膜形成用原料气化成为蒸气的步骤可在原料容器 内进行,也可在气化室内进行。任一情况下,本发明的薄膜形成用原 料在0~150℃蒸发是优选的。另外,于原料容器内或气化室内使薄膜 形成用原料气化成为蒸气时,原料容器内或气化室内的压力均为1~10000Pa是优选的。
本发明的薄膜的制造方法除了采用ALD法,通过上述输送供给方 法使薄膜形成用原料气化成蒸气,将该蒸气导入成膜腔室内的原料导 入步骤以外,也可具有通过该蒸气中的以上述通式(1)表示的化合物 于基体表面形成前体薄膜的前体薄膜成膜步骤,将未反应的薄膜形成 用原料排气的排气步骤,及使该前体薄膜与反应性气体化学反应,在 该基体表面形成含有金属的薄膜的含有金属的薄膜形成步骤。
以下,针对上述各步骤,以形成金属氧化物薄膜时为例详细说明。 通过ALD法形成金属氧化物薄膜时,首先进行前述说明的原料导入步 骤。使薄膜形成用原料成为蒸气时的优选温度或压力与上述说明的相 同。其次,通过导入堆积反应部的以通式(1)表示的化合物,于基体 表面成膜前体薄膜(前体薄膜成膜步骤)。此时,也可加热基体、或 加热堆积反应部而施加热。以该步骤成膜的前体薄膜为金属氧化物薄 膜、或以通式(1)表示的化合物的一部分分解及/或反应而生成的薄 膜,具有与目的的金属氧化物薄膜不同的组成。进行本步骤时的基体 温度在室温~500℃是优选的,更优选为150~350℃。进行本步骤时 的体系(成膜腔室内)的压力1~10000Pa是优选的,更优选为10~ 1000Pa。
其次,从堆积反应部排出未反应的薄膜形成用原料气体或副生的 气体(排气步骤)。未反应的薄膜形成用原料气体或副生的气体理想 上从堆积反应部完全排气,但并无必要必定完全排气。排气方法有通 过氮气、氦气、氩气等的惰性气体吹扫体系内的方法,通过使体系内 减压而排气的方法,组合这些方法等。减压时的减压度为0.01~300Pa 是优选的,更优选为0.01~100Pa。
其次,于堆积反应部导入氧化性气体,通过该氧化性气体的作用 或氧化性气体及热的作用,从以之前的前体薄膜成膜步骤所得的前体 薄膜形成金属氧化物薄膜(含有金属氧化物的薄膜形成步骤)。本步 骤中,作用热时的温度在室温~500℃是优选的,更优选为150~ 350℃。进行本步骤时的体系(成膜腔室内)的压力优选为1~10000Pa, 更优选为10~1000Pa。本发明的薄膜形成用原料与氧化性气体的反应 性良好,可获得金属氧化物薄膜。
本发明的薄膜的制造方法中,采用如上述的ALD法时,将由上述 的原料导入步骤、前体薄膜成膜步骤、排气步骤及含有金属氧化物的 薄膜形成步骤所成的一连串操作的薄膜堆积设为1个循环,可重复复 数次该循环直至获得必要膜厚的薄膜。该情况下,进行1个循环后, 优选与上述排气步骤同样地,从堆积反应部排出未反应的薄膜形成用 原料及反应性气体(形成金属氧化物薄膜时为氧化性气体)进而排出 副生的气体后,进行下1个循环。
另外,金属氧化物薄膜的通过ALD法的形成中,也可施加等离子 体、光、电压等的能量,也可使用催化剂。施加该能量时期及使用催 化剂时期并未特别限定,可以为例如于原料导入步骤中的本发明的薄 膜用形成用原料气体导入时、前体薄膜成膜步骤或含有金属氧化物的 薄膜形成步骤中的加温时、排气步骤的体系内排气时、含有金属氧化 物的薄膜形成步骤中的氧化性气体导入时,也可为上述各步骤之间。
另外,本发明的薄膜的制造方法中,薄膜堆积后,为了获得更良 好的电特性,也可于惰性环境下、氧化性环境下或还原性环境下进行 退火处理,于必须埋入阶差时,也可设回焊步骤。该情况的温度为 200~1000℃,优选为250~500℃。
使用本发明的薄膜形成用原料制造薄膜的装置可使用周知的化学 气相成长法用装置。具体的装置举例为例如图1所示的可通过冒泡供 给前体而进行的装置,或如图2所示的具有气化室的装置。而且,举 例为如图3及图4的可对反应性气体进行等离子体处理的装置。不限 于如图1~图4的单片式装置,也可使用利用批式炉可同时处理多数 片的装置。
使用本发明的薄膜形成用原料制造的薄膜,通过适当选择其他前 体、反应性气体及制造条件,可成为金属、氧化物陶瓷、氮化物陶瓷、 玻璃等的期望种类的薄膜。已知该薄膜显示各种电特性及光学特性等, 已应用于各种用途。例如,应用于半导体、太阳能电池、TFT等的用 途,其中,主要可使用作为半导体材料用的高介电材料。
[实施例]
以下列举实施例及评价例更详细说明本发明。然而,本发明不受 以下实施例的任何限制。
[实施例1]利用ALD法的氧化锆薄膜的制造
将化合物No.34作为化学气相成长用原料,使用图1所示的ALD 装置通过以下条件的ALD法,于形成直径220nm、深8600nm(宽高比 39.1)的沟的硅基板上制造氧化锆薄膜。针对所得薄膜,利用X射线反 射率法测定膜厚、利用FE-SEM的观察截面、利用X射线衍射法及X射线光电子分光法进行薄膜构造及薄膜组成的确认。沟所无法形成的 部分中薄膜的膜厚为3~6nm,且沟部分也以均匀的厚度形成薄膜。薄 膜的组成为氧化锆(利用XPS分析由Zr3d及Ols的峰确认),而且, 碳含量少于检测下限的0.1atom%。每1个循环所得的膜厚为0.02~ 0.04nm。
(条件)
反应温度(基板温度):210℃,反应性气体:臭氧
(步骤)
将由下述(1)~(4)所成的一连串步骤设为1个循环,重复150 个循环:
(1)导入于原料容器压热温度140℃、原料容器内压力10Pa的条 件气化的化学气相成长用原料的蒸气,以体系压20Pa堆积20秒;
(2)通过30秒的氩吹扫,去除未反应原料;
(3)导入反应性气体,以体系压力20Pa反应20秒;
(4)通过30秒的氩吹扫,去除未反应原料。
[比较例1]利用ALD法的氧化锆薄膜的制造
除了将下述的比较化合物1作为化学气相成长用原料以外,与以 实施例1同样的条件,尝试在硅基板上制造氧化锆薄膜。对于所得到 的薄膜,利用X射线反射率法测定膜厚、利用X射线衍射法及X射线 光电子分光法进行薄膜构造及薄膜组成的确认。沟所无法形成的部分 中薄膜的膜厚为3~4nm,但沟部分以不均匀的厚度形成薄膜(在沟的 底部中,是薄膜大致不形成的状态,除了在沟的底部以外,形成膜厚 3~6nm的薄膜)。薄膜的组成为氧化锆(利用XPS分析,以Zr3d及Ols 的峰确认),且薄膜中的碳含有量为8atom%。每1个循环所得的膜厚 为0.02~0.04nm。
[化9]
比较化合物1
[比较例2]利用ALD法的氧化锆薄膜的制造
除了将下述的比较化合物2作为化学气相成长用原料以外,与以 实施例1同样的条件,尝试在硅基板上制造氧化锆薄膜。对于所得到 的薄膜,利用X射线反射率法测定膜厚、利用X射线衍射法及X射线 光电子分光法进行薄膜构造及薄膜组成的确认。沟所无法形成的部分 中薄膜的膜厚为3~4nm,但沟部分以不均匀的厚度形成薄膜(在沟的 底部中,是薄膜大致不形成的状态,除了在沟的底部以外,形成膜厚 3~6nm的薄膜)。薄膜的组成为氧化锆(利用XPS分析,以Zr3d及Ols 的峰确认),且薄膜中的碳含有量为8atom%。每1个循环所得的膜厚 为0.02~0.04nm。
[化10]
比较化合物2
在实施例1中,可得到高品质的氧化锆薄膜。另外,化合物No.34 的热稳定性高,可知硅基板上的宽高比高的沟的部分也可形成均匀地 高品质的薄膜。另一方面,在比较例1及比较例2中,在硅基板上的 宽高比高的沟的部分,不能以均匀的厚度形成薄膜,且残留于薄膜中 的碳成分多,故可知不能得到高品质的氧化锆薄膜。
[实施例2]利用ALD法的氧化铪薄膜的制造
将化合物No.58作为化学气相成长用原料,使用图1所示的ALD 装置通过以下条件的ALD法,于形成直径220nm、深8600nm的沟的硅 基板上制造氧化铪薄膜。对所得薄膜,利用X射线反射率法测定膜厚、 利用FE-SEM观察截面、利用X射线衍射法及X射线光电子分光法进行 薄膜构造及薄膜组成的确认。沟所无法形成的部分中薄膜的膜厚为 3~6nm,且沟部分也以均匀的厚度形成薄膜。薄膜的组成为氧化铪(利 用XPS分析以Hf4f及Ols的峰确认),而且,薄膜中的碳含量少于检 测下限的0.1atom%。每1个循环所得的膜厚为0.02~0.04nm。
(条件)
反应温度(基板温度):280℃,反应性气体:臭氧
(步骤)
将由下述(1)~(4)所成的一连串步骤设为1个循环,重复 150个循环:
(1)导入于原料容器加热温度140℃、原料容器内压力10Pa的条 件气化的化学气相成长用原料的蒸气,以体系压20Pa堆积20秒;
(2)通过30秒的氩吹扫,去除未反应原料;
(3)导入反应性气体,以体系压力20Pa反应20秒;
(4)通过30秒的氩吹扫,去除未反应原料。
[实施例3]利用ALD法的氧化铪薄膜的制造
除了将化合物No.66作为化学气相成长用原料以外,与以实施例 2同样的条件,在硅基板上制造氧化铪薄膜。对于所得到的薄膜,利 用X射线反射率法测定膜厚、利用FE-SEM观察截面、利用X射线衍射 法及X射线光电子分光法进行薄膜构造及薄膜组成的确认。沟所无法 形成的部分中薄膜的膜厚为3~6nm,且沟部分以均匀的厚度形成薄 膜。薄膜的组成为氧化铪(利用XPS分析,以Hf4f及Ols的峰确认), 且薄膜中的碳含量少于检测下限的0.1atom%。每1个循环所得的膜厚 为0.02~0.04nm。
在实施例2及3中,每一个都可得到高品质的氧化铪薄膜。另外, 化合物No.58及66的热稳定性高,故可知硅基板上的宽高比高的沟的 部分也可形成均匀地高品质的薄膜。
需要说明的是,本国际申请主张基于2016年5月23日申请的日 本国专利申请第2016-102628号的优先权,且将该日本国际申请的全 内容援引加入本国际申请。
Claims (5)
2.如权利要求1的薄膜形成用原料,其是ALD法用薄膜形成用原料。
3.如权利要求1或2的薄膜形成用原料,其用于在宽高比为10~200的沟上形成薄膜。
4.一种薄膜的制造方法,其将含有使如权利要求1或2的薄膜形成用原料气化而得到的通式(1)表示的化合物的蒸气,导入设置有基体的成膜腔室内,使该化合物分解及/或使其进行化学反应而在该基体的表面形成含有选自钛、锆及铪中至少1种的原子的薄膜。
5.如权利要求4的薄膜的制造方法,其中,在前述基体上形成宽高比为10~200的沟。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016-102628 | 2016-05-23 | ||
JP2016102628A JP6796950B2 (ja) | 2016-05-23 | 2016-05-23 | 薄膜形成用原料及び薄膜の製造方法 |
PCT/JP2017/007483 WO2017203775A1 (ja) | 2016-05-23 | 2017-02-27 | 薄膜形成用原料及び薄膜の製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109154080A CN109154080A (zh) | 2019-01-04 |
CN109154080B true CN109154080B (zh) | 2021-05-11 |
Family
ID=60412261
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201780031611.4A Active CN109154080B (zh) | 2016-05-23 | 2017-02-27 | 薄膜形成用原料及薄膜的制造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10927460B2 (zh) |
JP (1) | JP6796950B2 (zh) |
KR (1) | KR20190009328A (zh) |
CN (1) | CN109154080B (zh) |
TW (1) | TWI761333B (zh) |
WO (1) | WO2017203775A1 (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10465289B2 (en) * | 2016-12-30 | 2019-11-05 | L'Air Liquide, Société Anonyme pour l'Etude at l'Exploitation des Procédés Georges Claude | Zirconium, hafnium, titanium precursors and deposition of group 4 containing films using the same |
JP7240903B2 (ja) * | 2019-03-05 | 2023-03-16 | レール・リキード-ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | インジウム化合物および該インジウム化合物を用いたインジウム含有膜の成膜方法 |
KR102627457B1 (ko) * | 2019-08-06 | 2024-01-19 | 삼성전자주식회사 | 나이오븀 화합물과 이를 이용하는 박막 형성 방법 |
JP7246284B2 (ja) * | 2019-08-15 | 2023-03-27 | 東京エレクトロン株式会社 | 成膜方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20140078534A (ko) * | 2012-12-17 | 2014-06-25 | 솔브레인씨그마알드리치 유한회사 | 금속 전구체 및 이를 이용하여 제조된 금속 함유 박막 |
CN103930431A (zh) * | 2011-03-15 | 2014-07-16 | 株式会社Mecharonics | 新型第4b族金属有机化合物及其制备 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101263454B1 (ko) | 2011-03-15 | 2013-11-27 | 주식회사 메카로닉스 | 지르코늄 금속을 함유하는 신규한 유기금속화합물 및 그 제조방법 |
KR101395644B1 (ko) * | 2012-02-08 | 2014-05-16 | 주식회사 메카로닉스 | 신규한 4-비이 족 금속 유기화합물 및 그 제조방법 |
KR102147190B1 (ko) * | 2015-03-20 | 2020-08-25 | 에스케이하이닉스 주식회사 | 막형성조성물 및 그를 이용한 박막 제조 방법 |
-
2016
- 2016-05-23 JP JP2016102628A patent/JP6796950B2/ja active Active
-
2017
- 2017-02-27 CN CN201780031611.4A patent/CN109154080B/zh active Active
- 2017-02-27 KR KR1020187036266A patent/KR20190009328A/ko not_active Application Discontinuation
- 2017-02-27 WO PCT/JP2017/007483 patent/WO2017203775A1/ja active Application Filing
- 2017-02-27 US US16/302,895 patent/US10927460B2/en active Active
- 2017-03-06 TW TW106107233A patent/TWI761333B/zh active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103930431A (zh) * | 2011-03-15 | 2014-07-16 | 株式会社Mecharonics | 新型第4b族金属有机化合物及其制备 |
KR20140078534A (ko) * | 2012-12-17 | 2014-06-25 | 솔브레인씨그마알드리치 유한회사 | 금속 전구체 및 이를 이용하여 제조된 금속 함유 박막 |
Also Published As
Publication number | Publication date |
---|---|
TWI761333B (zh) | 2022-04-21 |
TW201808970A (zh) | 2018-03-16 |
WO2017203775A1 (ja) | 2017-11-30 |
US20190292663A1 (en) | 2019-09-26 |
CN109154080A (zh) | 2019-01-04 |
US10927460B2 (en) | 2021-02-23 |
JP6796950B2 (ja) | 2020-12-09 |
JP2017210632A (ja) | 2017-11-30 |
KR20190009328A (ko) | 2019-01-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2014103588A1 (ja) | アルミニウム化合物、薄膜形成用原料及び薄膜の製造方法 | |
CN109154080B (zh) | 薄膜形成用原料及薄膜的制造方法 | |
US10882874B2 (en) | Vanadium compound | |
WO2018088078A1 (ja) | 化合物、薄膜形成用原料、原子層堆積法用の薄膜形成用原料及び薄膜の製造方法 | |
EP3643700A1 (en) | Metal alkoxide compound, thin-film-forming raw material, and method for producing thin film | |
WO2019097768A1 (ja) | ルテニウム化合物、薄膜形成用原料及び薄膜の製造方法 | |
CN110831950B (zh) | 钨化合物、薄膜形成用原料和薄膜的制造方法 | |
JP2018203641A (ja) | 新規な化合物、薄膜形成用原料及び薄膜の製造方法 | |
JP4107923B2 (ja) | イットリウム含有複合酸化物薄膜の製造方法 | |
CN115362282B (zh) | 原子层沉积法用薄膜形成用原料及薄膜的制造方法 | |
TWI824133B (zh) | 薄膜形成用原料、薄膜之製造方法及新穎的鈧化合物 | |
JP6116007B2 (ja) | 薄膜形成用原料及び薄膜の製造方法 | |
JP2018083771A (ja) | 化合物、薄膜形成用原料及び薄膜の製造方法 | |
WO2022196491A1 (ja) | スズ化合物、薄膜形成用原料、薄膜、薄膜の製造方法及びハロゲン化合物 | |
US20200131042A1 (en) | Raw material for thin film formation, method for manufacturing thin film, and novel compound | |
JP2021161520A (ja) | 薄膜形成原料、薄膜及びその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |