JP7185394B2 - スズ化合物、その合成方法、ald用スズ前駆体化合物、及びスズ含有物質膜の形成方法 - Google Patents
スズ化合物、その合成方法、ald用スズ前駆体化合物、及びスズ含有物質膜の形成方法 Download PDFInfo
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- JP7185394B2 JP7185394B2 JP2017232967A JP2017232967A JP7185394B2 JP 7185394 B2 JP7185394 B2 JP 7185394B2 JP 2017232967 A JP2017232967 A JP 2017232967A JP 2017232967 A JP2017232967 A JP 2017232967A JP 7185394 B2 JP7185394 B2 JP 7185394B2
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- 150000001875 compounds Chemical class 0.000 title claims description 107
- 238000000034 method Methods 0.000 title claims description 80
- 239000002243 precursor Substances 0.000 title claims description 77
- 239000000463 material Substances 0.000 title claims description 51
- 150000003606 tin compounds Chemical class 0.000 title description 25
- 230000002194 synthesizing effect Effects 0.000 title description 6
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- 239000010408 film Substances 0.000 claims description 109
- 238000000231 atomic layer deposition Methods 0.000 claims description 51
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 35
- 229910001887 tin oxide Inorganic materials 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- -1 amine compound Chemical class 0.000 claims description 19
- 239000000376 reactant Substances 0.000 claims description 19
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 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
- VKJLWXGJGDEGSO-UHFFFAOYSA-N barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ba+2] VKJLWXGJGDEGSO-UHFFFAOYSA-N 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
- 239000001273 butane Substances 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
- 239000007833 carbon precursor Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 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
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 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
- 230000006866 deterioration Effects 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000004984 dialkylaminoalkoxy group Chemical group 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003292 glue Substances 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
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 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
- SDAXRHHPNYTELL-UHFFFAOYSA-N heptanenitrile Chemical compound CCCCCCC#N SDAXRHHPNYTELL-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 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
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 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
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical class [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001272 nitrous oxide Substances 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
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- KJXBRHIPHIVJCS-UHFFFAOYSA-N oxo(oxoalumanyloxy)lanthanum Chemical compound O=[Al]O[La]=O KJXBRHIPHIVJCS-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 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
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- ASRAWSBMDXVNLX-UHFFFAOYSA-N pyrazolynate Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=O)C=1C(C)=NN(C)C=1OS(=O)(=O)C1=CC=C(C)C=C1 ASRAWSBMDXVNLX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 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
- 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
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- CZXRMHUWVGPWRM-UHFFFAOYSA-N strontium;barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Sr+2].[Ba+2] CZXRMHUWVGPWRM-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 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
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C07F7/22—Tin compounds
- C07F7/2284—Compounds with one or more Sn-N linkages
-
- 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
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
- Semiconductor Memories (AREA)
Description
SnX2R2+2LiNQ2→Sn(NQ2)2R2+2LiX 反応式II
ここで、Xは、フッ素(F)、塩素(Cl)、臭素(Br)、及びヨード(I)から構成される群から選択される1種以上であり、RとQは、それぞれ独立して、C1-C4の直線状または分枝状のアルキル基である。
本発明の技術的思想によるスズ化合物は、下記化学式Iによっても表示される。
以下では、前記化学式Iのスズ化合物を合成する方法について説明する。
ここで、Xは、フッ素(F)、塩素(Cl)、臭素(Br)及びヨード(I)から構成される群から選択される1種以上であり、1つのSnに結合された4つのXは、互いに同じであってもよく、異なっていてもよい。また、Rは、C1-C4の直線状または分枝状のアルキル基であり、例えば、1つのSnに結合された4つのRは、互いに同じであってもよく、異なっていてもよい。
ここで、Qは、C1-C4の直線状または分枝状のアルキル基であり、例えば、1つの窒素(N)に結合された2つのQは、互いに同じであってもよく、異なっていてもよい。
前述のスズ化合物は、スズを含む物質膜(以下、「スズ含有物質膜」とする)、例えば、スズ金属膜、スズ酸化膜、スズ窒化膜、スズ酸窒化膜またはスズ酸素炭素窒化膜を形成するためのスズ前駆体化合物としても利用される。以下では、原子層蒸着方法によって、スズ酸化物層を形成する方法を中心に説明する。当業者であるならば、類似の方式によって、スズ金属膜、スズ窒化層、スズ酸窒化膜またはスズ酸素炭素窒化膜を形成することができるということを理解するであろう。
以上では、前記スズ含有物質膜がALDによって形成されるということを例示したが、前記スズ前駆体化合物は、化学気相蒸着(CVD:chemical vapor deposition)のための前駆体物質としても利用される。
シングルソース法の場合は、前記他の前駆体として、熱及び/または酸化分解の挙動が本発明の技術的思想によるスズ前駆体化合物と類似した化合物を使用することができる。また、前記カクテルソース法の場合は、前記他の前駆体として、熱及び/または酸化分解の挙動が本発明の技術的思想によるスズ前駆体化合物と類似しており、混合時、化学反応などによる変質を起こさないものを使用することが適する。
本発明の技術的思想による薄膜形成方法によって製造されたスズ含有物質膜は、多様な用途に使用される。例えば、前記スズ含有物質膜は、トランジスタのゲート、金属配線、例えば、銅配線に使用される導電性バリア膜、三次元CTF(charge trap flash)セルに含まれたゲート誘電膜のトンネルバリア膜、液晶用バリア金属膜、薄膜太陽電池用部材、半導体設備用部材、ナノ構造体などにも使用されるが、前記スズ含有物質膜の用途は、前述の素子に限定されるものではない。
化合物Sn[N( i Pr) 2 ] 2 Me 2 の合成
1,000mlフラスコに、SnCl4 100g(0.35モル)及びn-ヘキサン300mlを入れて混合した。アイスバス(ice bath)下で、Sn(Me)4 81.4g(0.455モル)を徐々に添加した。約2時間撹拌し、SnMe2Cl2の合成を完了した。
(分析値)
1H NMR(C6D6):δ 3.42(st,4H、)、1.12(d,24H)、0.38(s,6H)
<評価例1>
化合物Sn[N( i Pr) 2 ] 2 Me 2 の特性評価
図7は、実験例1で得られた化合物Sn[N(iPr)2]2Me2の熱重量分析(TGA:thermogravimetric analysis)結果を示したグラフである。化合物Sn[N(iPr)2]2Me2を10mg取り、アルゴン雰囲気で分当たり10℃の昇温条件にして分析した。
原子層蒸着法(ALD)によって、シリコン基板上にスズ酸化物薄膜を製造した。
化合物Sn[N(Me) 2 ] 2 Me 2 の合成
1,000mlフラスコに、SnCl4 117g(0.45モル)及びn-ヘキサン300mlを入れて混合した。アイスバス内のフラスコに、Sn(Me)4 81.4g(0.455モル)を徐々に添加した。約2時間撹拌し、SnMe2Cl2の合成を完了した。
1H NMR(C6D6):δ 2.76(s,12H)、0.09(s,6H)
<実験例4>
化合物Sn[N(iPr)2]2Me2の代わりに、化合物Sn[N(Me)2]2Me2を利用する以外には、実験例2と同一方法でスズ酸化物の薄膜を形成し、1サイクル当たりスズ酸化物の蒸着厚を各蒸着温度別に測定し、図12に示した。
化合物Sn[N(Me) 2 ] 4 の合成
1,000mlフラスコに、SnCl4 100g(0.35モル)及びn-ヘキサン300mlを入れて混合した。アイスバス内のフラスコに、リチウムジメチルアミド(Li-DMA)80g(1.57モル)をエチルエーテルに希釈して徐々に添加し、常温で8時間撹拌して反応を完了した。反応が完了した後、生成物を濾過することによりLiCl塩を除去して得られた溶液から、減圧下で溶媒及び副生成物を除去した。溶媒を除去した後で精製し、化合物Sn[N(Me)2]4を63g得た(収率:70%)。
1H NMR(C6D6):δ 2.79(s,24H)
スズ酸化物薄膜の形成
化合物Sn[N(iPr)2]2Me2の代わりに、化合物Sn[N(Me)2]4を利用する以外には、実験例2と同一方法でスズ酸化物の薄膜を形成し、1サイクル当たりのスズ酸化物の蒸着厚を各蒸着温度別に測定し、図13に示した。
化合物Sn[N(iPr)2]2Me2の代わりに、化合物Sn(Me)4を利用する以外には、実験例2と同一方法でスズ酸化物の薄膜を形成し、1サイクル当たりのスズ酸化物の蒸着厚を各蒸着温度別に測定し、図14に示した。化合物Sn(Me)4は、シグマ-アルドリッチ(Sigma-Aldrich)社の製品であり、95%グレードを購入して使用した。
110a モノレイヤー
110 スズ含有物質膜
Claims (11)
- 前記反応物は、O2、O3、プラズマO2、H2O、NO2、NO、N2O、CO2、H2O2、HCOOH、CH3COOH、(CH3CO)2O、またはそれらの混合物を含み、
前記スズ物質膜は、スズ酸化物膜である、請求項1に記載のスズ含有物質膜の形成方法。 - 前記スズ酸化物膜は、ルチル結晶相を含む、請求項2に記載のスズ含有物質膜の形成方法。
- 前記反応物は、NH3、モノアルキルアミン、ジアルキルアミン、トリアルキルアミン、有機アミン化合物、ヒドラジン化合物、またはそれらの混合物であり、
前記スズ物質膜は、スズ窒化物膜であることを特徴とする請求項1に記載のスズ含有物質膜の形成方法。 - 前記スズ前駆体化合物は、少なくとも270℃~350℃の温度範囲又はQ 1 ~Q 4 がメチル基の場合、温度が270℃~320℃で、一定原子層蒸着速度を有する、請求項1に記載のスズ含有物質膜の形成方法。
- 前記スズ前駆体化合物は、少なくとも270℃~320℃の温度範囲で、一定原子層蒸着速度を有する、請求項1に記載のスズ含有物質膜の形成方法。
- 前記スズ含有物質膜内に、ハロゲン元素を含まない、請求項1~6のいずれか一項に記載のスズ含有物質膜の形成方法。
- 反応空間内の基板上に、前記化学式Iの構造を有するスズ前駆体化合物のモノレイヤーを形成する段階において、前記基板上に、前記化学式Iの構造を有するスズ前駆体化合物を1秒~100秒間供給する、請求項1~7のいずれか一項に記載のスズ含有物質膜の形成方法。
- 前記スズ含有物質膜が、導電性バリア膜、ゲート誘電膜のトンネルバリア膜、液晶用バリア金属膜、薄膜太陽電池用部材、半導体設備用部材及びナノ構造体のうちいずれか一つである、請求項1~8のいずれか一項に記載のスズ含有物質膜の形成方法。
- 前記反応物は、O2、O3、プラズマO2、H2O、NO2、NO、N2O、CO2、H2O2、HCOOH、CH3COOH、(CH3CO)2O、またはそれらの混合物を含み、
前記スズ含有物質膜は、スズ酸化物膜である、請求項10に記載のスズ含有物質膜の形成方法。
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