TW201406984A - 用於ald/cvd方法的gst膜前驅物 - Google Patents
用於ald/cvd方法的gst膜前驅物 Download PDFInfo
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- TW201406984A TW201406984A TW102129057A TW102129057A TW201406984A TW 201406984 A TW201406984 A TW 201406984A TW 102129057 A TW102129057 A TW 102129057A TW 102129057 A TW102129057 A TW 102129057A TW 201406984 A TW201406984 A TW 201406984A
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- Prior art keywords
- group
- hydrazine
- alkyl
- ruthenium
- alkenyl
- Prior art date
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- 239000002243 precursor Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 56
- 230000008569 process Effects 0.000 title abstract description 17
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 12
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 10
- -1 lanthanum alkoxide Chemical class 0.000 claims description 84
- 125000003118 aryl group Chemical group 0.000 claims description 56
- 229910052707 ruthenium Inorganic materials 0.000 claims description 55
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 48
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- 239000010410 layer Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 33
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 31
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 31
- 230000008021 deposition Effects 0.000 claims description 28
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 26
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 24
- 125000003342 alkenyl group Chemical group 0.000 claims description 24
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 24
- 125000006717 (C3-C10) cycloalkenyl group Chemical group 0.000 claims description 21
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- 229910052738 indium Inorganic materials 0.000 claims description 13
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 125000003158 alcohol group Chemical group 0.000 claims description 7
- 229910052732 germanium Inorganic materials 0.000 claims description 7
- 229910052762 osmium Inorganic materials 0.000 claims description 7
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QQEWMMRFXYVLQU-UHFFFAOYSA-N decylhydrazine Chemical compound CCCCCCCCCCNN QQEWMMRFXYVLQU-UHFFFAOYSA-N 0.000 claims description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- WMOJAWPGEQWAMM-UHFFFAOYSA-N [Ir].[Ru].[Ru] Chemical compound [Ir].[Ru].[Ru] WMOJAWPGEQWAMM-UHFFFAOYSA-N 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 229910000929 Ru alloy Inorganic materials 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 239000002052 molecular layer Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 2
- LUEJXANRWNZDGH-UHFFFAOYSA-N CC(C)(C)CCCCCCCCCPCCCCCCCCCC(C)(C)C Chemical group CC(C)(C)CCCCCCCCCPCCCCCCCCCC(C)(C)C LUEJXANRWNZDGH-UHFFFAOYSA-N 0.000 claims 1
- LWUZVGFCSKAGKJ-UHFFFAOYSA-N CCC(CC)(CC)CCCCCCCCCPCCCCCCCCCC(CC)(CC)CC Chemical compound CCC(CC)(CC)CCCCCCCCCPCCCCCCCCCC(CC)(CC)CC LWUZVGFCSKAGKJ-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000003282 alkyl amino group Chemical group 0.000 claims 1
- NHLNJPXVJOFRNH-UHFFFAOYSA-N ethanol germanium(4+) Chemical compound [Ge+4].CCO.CCO.CCO.CCO NHLNJPXVJOFRNH-UHFFFAOYSA-N 0.000 claims 1
- 229910052747 lanthanoid Inorganic materials 0.000 claims 1
- 150000002602 lanthanoids Chemical class 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 238000000231 atomic layer deposition Methods 0.000 abstract description 37
- 229910000618 GeSbTe Inorganic materials 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 abstract description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052714 tellurium Inorganic materials 0.000 abstract description 2
- KFMLSKLCIQLEQK-UHFFFAOYSA-N [SiH3].[Sb] Chemical compound [SiH3].[Sb] KFMLSKLCIQLEQK-UHFFFAOYSA-N 0.000 abstract 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract 2
- 229910001245 Sb alloy Inorganic materials 0.000 abstract 1
- GTVXHILVUZHIHQ-UHFFFAOYSA-N [SiH3][Bi] Chemical compound [SiH3][Bi] GTVXHILVUZHIHQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002140 antimony alloy Substances 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 229910052715 tantalum Inorganic materials 0.000 description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- INFRJEOPIATYJB-UHFFFAOYSA-N 3-methoxy-2,2-dimethyldecane Chemical compound COC(C(C)(C)C)CCCCCCC INFRJEOPIATYJB-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 206010036790 Productive cough Diseases 0.000 description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 210000003298 dental enamel Anatomy 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 150000003304 ruthenium compounds Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 210000003802 sputum Anatomy 0.000 description 4
- 208000024794 sputum Diseases 0.000 description 4
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 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 3
- 238000011049 filling Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZQBSPSZMRYBLLZ-UHFFFAOYSA-N CC(CCCCCCCCCCl)(C)C Chemical compound CC(CCCCCCCCCCl)(C)C ZQBSPSZMRYBLLZ-UHFFFAOYSA-N 0.000 description 2
- ZXXKIYZOZANGNS-UHFFFAOYSA-N CC(CCCCCCCCCP(CCCCCCCCCC(C)(C)C)CCCCCCCCCC(C)(C)C)(C)C Chemical compound CC(CCCCCCCCCP(CCCCCCCCCC(C)(C)C)CCCCCCCCCC(C)(C)C)(C)C ZXXKIYZOZANGNS-UHFFFAOYSA-N 0.000 description 2
- YLUZQMOLMHKGJC-UHFFFAOYSA-N CCC(CC)(CC)CCCCCCCCCP(CCCCCCCCCC(CC)(CC)CC)CCCCCCCCCC(CC)(CC)CC Chemical compound CCC(CC)(CC)CCCCCCCCCP(CCCCCCCCCC(CC)(CC)CC)CCCCCCCCCC(CC)(CC)CC YLUZQMOLMHKGJC-UHFFFAOYSA-N 0.000 description 2
- CQXGHOZCKJZMOW-UHFFFAOYSA-N CCCCCCCCCCC1=C(C2=C(C(=C1C)C)C3=C(C(=C(C(=C3C2)C)C)C)C)CCCCCCCCCC Chemical compound CCCCCCCCCCC1=C(C2=C(C(=C1C)C)C3=C(C(=C(C(=C3C2)C)C)C)C)CCCCCCCCCC CQXGHOZCKJZMOW-UHFFFAOYSA-N 0.000 description 2
- WUGIHIDKVSDYPA-UHFFFAOYSA-N CNN(C)C.NN Chemical compound CNN(C)C.NN WUGIHIDKVSDYPA-UHFFFAOYSA-N 0.000 description 2
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229910006107 GeBiTe Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
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- 230000008859 change Effects 0.000 description 2
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- 230000017525 heat dissipation Effects 0.000 description 2
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 2
- 229910000103 lithium hydride Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- HWJHZLJIIWOTGZ-UHFFFAOYSA-N n-(hydroxymethyl)acetamide Chemical compound CC(=O)NCO HWJHZLJIIWOTGZ-UHFFFAOYSA-N 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000012782 phase change material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000012552 review Methods 0.000 description 2
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- CTCLBKUMUYDNOW-UHFFFAOYSA-N 1,2-di(nonyl)-9h-fluorene Chemical compound C1=CC=C2C3=CC=C(CCCCCCCCC)C(CCCCCCCCC)=C3CC2=C1 CTCLBKUMUYDNOW-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- YVKNZKRTDFOBNO-UHFFFAOYSA-N 3-methoxy-2,2-dimethylundecane Chemical compound CC(C(OC)CCCCCCCC)(C)C YVKNZKRTDFOBNO-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- IKKDHXKSRJBGGO-UHFFFAOYSA-N CC(CCCCCCCCCNNCCCCCCCCCC(C)(C)C)(C)C Chemical compound CC(CCCCCCCCCNNCCCCCCCCCC(C)(C)C)(C)C IKKDHXKSRJBGGO-UHFFFAOYSA-N 0.000 description 1
- LJJHROSYCPMGJY-UHFFFAOYSA-N CCC(CC)(CC)CCCCCCCCCNNCCCCCCCCCC(CC)(CC)CC Chemical compound CCC(CC)(CC)CCCCCCCCCNNCCCCCCCCCC(CC)(CC)CC LJJHROSYCPMGJY-UHFFFAOYSA-N 0.000 description 1
- DRRKAOITJFLWET-UHFFFAOYSA-N CN(C)C(C(C)(C)C)CCCCCCC Chemical compound CN(C)C(C(C)(C)C)CCCCCCC DRRKAOITJFLWET-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- 229910005936 Ge—Sb Inorganic materials 0.000 description 1
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- NIBNUNQXBQSRRC-UHFFFAOYSA-M [O-2].[OH-].O.O.O.[In+3] Chemical compound [O-2].[OH-].O.O.O.[In+3] NIBNUNQXBQSRRC-UHFFFAOYSA-M 0.000 description 1
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- MRPWWVMHWSDJEH-UHFFFAOYSA-N antimony telluride Chemical compound [SbH3+3].[SbH3+3].[TeH2-2].[TeH2-2].[TeH2-2] MRPWWVMHWSDJEH-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- 238000011010 flushing procedure Methods 0.000 description 1
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- 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 1
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical group [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910052696 pnictogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 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 1
- MJUXBCICAGPQDB-UHFFFAOYSA-N triethoxysulfanium Chemical compound CCO[S+](OCC)OCC MJUXBCICAGPQDB-UHFFFAOYSA-N 0.000 description 1
- 238000001845 vibrational spectrum Methods 0.000 description 1
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Abstract
本發明係利用選自由原子層沉積及化學氣相沉積所組成的群組的方法製造鍺-銻-碲合金(GST)或鍺-鉍-碲(GBT)膜的方法,其中把矽烷基銻前驅物當作該合金膜的銻來源使用。本發明也關於利用選自由原子層沉積及化學氣相沉積所組成的群組的方法藉由其他元素製造銻合金的方法,其中把矽烷基銻或矽烷基鉍前驅物當作銻或鉍的來源使用。
Description
本專利案係2009年1月16日申請的美國專利申請案序號第12/355,325號的連續案,其接著請求2008年1月28日申請的美國臨時專利申請案第61/023,989號在35 U.S.C.§119(e)保護之下的優先權益。
本發明係利用選自由原子層沉積及化學氣相沉
積所組成的群組的方法製造鍺-銻-碲合金(GST)或鍺-鉍-碲(GBT)膜的方法。
如同脫穎而出的技術,相變化材料對其於製造新型高積體、非揮發性記憶裝置:相變化隨機存取記憶體(PRAM),方面之應用引來越來越多關心。相變化隨機存取記憶(PRAM)裝置係利用於結晶相與非晶相之間進行可逆相變化的材料合成,該結晶相和非晶相具有截然不同的阻抗。最常使用的相變化材料是14族和15族元素的硫族化合物(chalcogenide)的三元組合物,例如鍺-銻-碲化合物(通常縮寫成GST)。
在設計PRAM電池時的工藝障礙之一是為了克
服GST材料於特定溫度下從結晶態切換至非晶態期間的散熱現象,必須施以大量復歸電流。此散熱現象能藉由將該GST材料侷限於接觸栓(contact plug)而大幅縮減,那將會降低動作所需的復歸電流。為了在基材上建立GST柱塞,而使用原子層沉積(ALD)法製造具有高保形性和化學組成均一性的膜。
相關先前技藝包括:Sang-Wook Kim, S. Sujith, Bun Yeoul Lee, Chem. Commun., 2006, pp 4811-4813.
Stephan Schulz, Martin Nieger, J. Organometallic Chem., 570, 1998, pp 275-278.
Byung Joon Choi, et al. Chem Mater. 2007, 19, pp 4387-4389; Byung Joon Choi, et al. J. Electrochem. Soc., 154, pp H318-H324 (2007); Ranyoung Kim, Hogi Kim, Soongil Yoon, Applied Phys. Letters, 89, pp 102-107 (2006).
Junghyun Lee, Sangjoon Choi, Changsoo Lee, Yoonho Kang, Daeil Kim, Applied Surface Science, 253 (2007) pp 3969-3976.
G. Becker, H. Freudenblum, O. Mundt, M. reti, M. Sachs, Synthetic Methods of Organometallic and Inorganic Chemistry, vol. 3, H.H. Karsch, New York, 1996, p. 193.
Sladek, A., Schmidbaur, H., Chem. Ber. 1995, 128, pp 565-567.
美國專利及專利申請案:
US 2006/0049447 A1 US 2006/0039192 A1;US 2006/0072370 A1;US 2006/0172083 A1;US 8,148,197;US 2012/171812 A1;及US 7,817,464.
在一方面中,本發明提供一種用於將含銻膜製造於基材表面上之ALD方法,該方法包含下列步驟:把烷氧化鍺當作前驅物引進沉積艙,其中該烷氧化鍺係由式Ge(OR14)4來表示,其中R14係C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團,以形成烷氧化鍺的分子層於該基材表面上;及把選自由下列所組成的群組之矽烷基銻前驅物引進該沉積艙:
在此R1-10個別為氫原子、C1-C10烷基、C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團;R11及R12個別為C1-C10烷基或C3-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團,以形成Sb層於該Te層頂部上,其中該Sb包含甲矽烷基取代基。
在另一方面中,本發明提供一種用於將鍺-鉍-碲合金膜製造於基材表面上之ALD方法,該方法包含下列步驟:把烷氧化鍺當作前驅物引進沉積艙,其中該烷氧化鍺係由式Ge(OR14)4來表示,其中R14係C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團,以形成烷氧化鍺的分子層於該基材表面上;及把選自由下列所組成的群組之碲前驅物引進該沉積艙:
在此R1、R2、R3、R4、R5及R6獨立地為氫、C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團,以與該烷氧化鍺層反應形成包含Te-Ge鍵的Te層,其中該Te包含甲矽烷基取代基;使該Te上的甲矽烷基取代基反應以與(i)水及/或(ii)具有通式ROH的醇形成Te-H鍵,在此R係C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團;把選自由下列所組成的群組之矽烷基銻前驅物引進該沉積艙:
在此R1-10個別為氫原子、C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團,以形成Sb層於該Te層上,其中該Bi包含甲矽烷基取代基;及使該Bi上的取代基反應以與(i)水及/或(ii)具有通式ROH的醇形成Bi-H鍵,在此R係C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團。
在又另一方面中,本發明提供一種用於將含銻-或鉍-膜製造於基材表面上之ALD方法,該方法包含下列步驟:把選自由下列所組成的群組之矽烷基銻或鉍前驅物引進沉積艙:
在此R1-10個別為氫原子、如分支或環狀鏈的帶1至10個碳的烷基或烯基或芳香族基團;R11及R12個別為C1-C10烷基或
C3-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團,以形成矽烷基銻單層;及把選自由下列所組成的群組的第二前驅物引進該沉積艙:M(OR13)3,其中M=Ga、In、Sb及Bi;而且R13係C1-C10烷基、C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團,M(OR13)3-xLx,其中M=Sb或Bi;L係選自Cl、Br、I或其混合物;x係0、1或2,附帶條件為當M=Sb時x不能為0;而且R13係C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團,M(OR14)4-xLx,其中M係選自由Ge、Sn、Pb所組成的群組;L係選自Cl、Br、I或其混合物;x係0、1、2或3;R14係C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團,M(NR14R15)3-xLx,其中M係選自由Sb、Bi、Ga、In所組成的群組;L係選自Cl、Br、I或其混合物;x係1、2或3;R14係C1-C10烷基或C3-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團;而且R15係選自由氫、C1-C10烷基或C3-C10烯基、C3-C10環狀基團、C3-C10環烯基或C4-C10芳香族基團所組成的群組,及M(NR14R15)4-xLx,其中M係選自由Ge、Sn、Pb所組成的群組;L係選自Cl、Br、I或其混合物;x係1、2或3;R14係C1-C10烷基或C3-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團;而且R15係選自由氫、C1-C10烷基或C3-C10烯基、C3-C10
環狀基團、C3-C10環烯基或C4-C10芳香族基團所組成的群組。
本發明關於一類的銻或鉍前驅物,其按照ALD方法產生銻層。該銻或鉍或銻-鉍合金層與隨後按照ALD循環沉積的鍺和碲層反應以形成GST適用於PRAM裝置的三元材料膜。
PRAM裝置中的GST或GBT材料正常在180°至300℃的溫度範圍中沉積。已發現於200℃下沉積的膜具有化學和結構性質。該ALD方法需要具有高化學反應性及反應選擇性的前驅物。現有的前驅物,例如二烷基碲、烷基銻及烷基鍺烷類於ALD循環使用的條件下沒有必需反應性。電漿常用以促成此沉積。
本發明提供矽烷基銻化合物當作ALD前驅物,其與醇類或水反應以產生銻層。憑藉著隨後從四胺基鍺和有機碲前驅物沉積鍺和碲,GST或GBT膜可以高保形性沉積於基材上。
本發明關於於ALD方法中產生銻層的矽烷基銻或矽烷基鉍前驅物。該銻或鉍層與隨後沉積的鍺和碲層於多數ALD循環中反應以形成適用於PRAM裝置的GST或GBT三元材料膜。在特定具體實施例中,本發明揭示數種具有高反應性和熱安定性的矽烷基銻前驅物及能用於ALD方法的化學性質以聯合其他化學藥品沉積GST或GBT膜。
在其他具體實施例中,本發明提供矽烷基銻或矽
烷基鉍化合物當作ALD前驅物,其與醇類或水反應以產生銻原子層。憑藉著隨後從四胺基鍺和碲前驅物沉積鍺和碲,GST膜可以高保形性沉積於基材上。
在特定具體實施例中,該銻或鉍前驅物包括選自由下列所組成的群組的三矽烷基銻、二矽烷基烷基銻、二矽烷基銻或二矽烷基胺基銻:
在此R1-10個別為氫原子、如分支或環狀鏈的帶1至10個碳的烷基或烯基或芳香族基團;R11及R12個別為C1-C10烷基或C3-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團。在特定具體實施例中,R1係氫原子、C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團。較佳地若在結構(A)中,R1-9之其一係芳香族,則於帶該芳香族的矽上的剩餘R1-9不是甲基。
在整個描述當中,該措辭“烷基”表示具有1至10或1至6個碳原子的線性或分支官能基。例示性烷基包括,但不限於,甲基、乙基、丙基、異丙基、丁基、異丁基、第
二丁基、第三丁基、戊基、異戊基、第三戊基、己基、異己基及新己基。在特定具體實施例中,該烷基可具有一或更多接附於彼的官能基例如,但不限於,烷氧基、二烷基胺基或其組合。在其他具體實施例中,該烷基沒有一或更多接附於彼的官能基。該措辭“環狀烷基”表示具有3至10或4至10個碳原子或5至10個碳原子的環狀官能基。例示性環烷基包括,但不限於,環丁基、環戊基、環己基及環辛基。該措辭“芳香族”表示具有4至10個碳原子或6至10個碳原子的芳香族環狀官能基。例示性芳基包括,但不限於,苯基、苯甲基、氯苯甲基、甲基基及鄰-二甲苯基。該措辭“烯基”表示具有一或更多碳-碳雙鍵並且具有2至10或2至6個碳原子或2至4個碳原子。
例示性三矽烷基銻或三矽烷基鉍前驅物包括,舉例來說,三(三甲基矽烷基)銻、三(三乙基矽烷基)銻及三(第三丁基二甲基矽烷基)銻、三(三甲基矽烷基)鉍、三(三乙基矽烷基)鉍及三(第三丁基二甲基矽烷基)鉍、叁(二甲基矽烷基)銻。
矽烷基銻或矽烷基鉍化合物與醇類或水具有高反應性。此反應於低溫下產生元素銻或鉍:
在其他本發明的具體實施例中,金屬銻或銻合金藉由使此類矽烷基銻或矽烷基鉍化合物與金屬化合物、烷氧化物及/或混合的鹵化物和烷氧化物化合物反應而沉積。金屬烷氧化物包括式M(OR13)3所示的化合物,其中M=Ga、In、Sb及Bi;而且R13係C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團。混合的金屬鹵化物和烷氧化物包括式M(OR13)3-xLx所示的化合物,其中M=Ga、In、Sb及Bi;L係選自Cl、Br、I或其混合物;x係0、1或2;而且R13與以上定義相同。這樣的化合物的實例包括,舉例來說,SbCl(OMe)2、SbCl2(OMe)、SbBr(OMe)2、SbBr2(OMe)、SbI(OMe)2、SbCl(OEt)2、SbCl2(OEt)、SbCl(OPri)2、SbCl2(OPri)、BiCl(OMe)2、BiCl2(OMe)、BiCl(OEt)2、BiCl2(OEt)、BiCl(OPri)2、BiCl2(OPri)。
這些反應能如以下證明於室溫至400℃的溫度範圍下發生。
在ALD方法中,該等矽烷基銻前驅物、醇類、鍺及碲前驅物,例如Ge(OMe)4和(Me3Si)2Te(其中“Me”係甲基),係以環狀方式藉由蒸氣牽引(vapor draw)或直接液體注射(DLI)引至沉積艙。沉積溫度較佳為介於室溫度與400℃之間。
沉積GBT膜的ALD反應能藉由下列機構舉例說明:
步驟1. 引進肆(甲氧基)鍺烷並且形成烷氧基鍺烷分子層於該基材表面上。
步驟2. 使六甲基二矽烷基碲與胺基鍺烷層反應以形成Te-Ge鍵伴隨二甲基胺基三甲基矽烷的消除。形成具有甲矽烷基取代基的Te層。
步驟3. 使甲醇與該碲層上剩餘的甲矽烷基反應以形成Te-H鍵及經由洗淨移除的揮發性副產物(甲氧基三甲基矽烷)。
步驟4. 引進叁(三甲基矽烷基)鉍並且形成鉍層於該碲層頂部上。
步驟5. 使甲醇與該鉍層上剩餘的甲矽烷基反應以形成Bi-H鍵及經由洗淨移除的揮發性副產物(甲氧基三甲基矽烷)。
步驟6. 再引進六甲基二矽烷基碲並且形成碲層。
步驟7. 再引進甲醇以移除該碲上的甲矽烷基。
另一ALD反應能藉由下列用於沉積Ge-Te-Ge-Sb或Ge-Te-Ge-Bi膜的機構來舉例說明:
步驟1. 引進肆(甲氧基)鍺烷並且形成烷氧基鍺烷分子層於該基材表面上.
步驟2. 使六甲基二矽烷基碲與烷氧基鍺烷層反應以形成Te-Ge鍵伴隨甲氧基三甲基矽烷的消除。形成具有甲矽烷基取代基的Te層。
步驟3. 使肆(甲氧基)鍺烷與該層上剩餘的甲矽烷基反應以利用矽烷基銻或矽烷基鉍隨著甲氧基三甲基矽烷的消除形成Te-Ge鍵。形成具有甲氧基取代基的Ge層。
步驟4. 引進叁(三甲基矽烷基)銻或叁(三甲基矽烷基)鉍以經由甲氧基三甲基矽烷的消除形成具有甲矽烷基取代基的銻層於該鍺層頂部上。
步驟5. 使肆(甲氧基)鍺烷與該Sb或Bi層上剩餘的甲矽烷基反應以形成Sb-Ge或Bi-Ge鍵,產生具有甲氧基取代基的Ge層。
接著重複進行ALD循環,可能許多次,直到達成所欲的膜厚度為止。下一個循環再藉由步驟1開始,等等。在另一具體實施例中,步驟2和步驟4能切換,亦即,仰賴待沉積的到底是Ge-Sb-Ge-Te或Ge-Bi-Ge-Te膜。
在特定具體實施例中,此方法中使用的矽烷基銻或矽烷基鉍化合物係選自由下列所組成的群組:
在此R1-10個別為氫原子、C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團。在特定具體實施例中,R1係氫原子、C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團。R11及R12個別為C1-C10烷基或C3-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團。較佳地若在結構(A)中,R1-9之其一係芳香族,則於帶該芳香族的矽上的剩餘R1-9不是甲基。再者,
較佳地,若在結構(A)中R1-9之任一係C1-3或苯基,則R1-9不能全為相同。
此方法中使用的烷氧基鍺烷類具有下列通式:
在此R1係氫原子、C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團。
在本發明又另一具體實施例中,GST膜能藉由使用鍺化合物當作前驅物而形成,其中該兼具鹵基和烷氧基配位子的鍺化合物係由此式Ge(OR14)4-xLx表示,其中L係選自Cl、Br、I或其混合物;x係0、1、2或3;R14係C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團。該鍺化合物前驅物能與,舉例來說,矽烷基銻、矽烷基鉍或矽烷基碲按照與上述M(OR13)3-xLx的相同方式反應。兼具鹵基和烷氧基配位子的鍺化合物的實例包括,舉例來說,GeCl(OMe)3、GeCl2(OMe)2、GeCl3(OMe)、GeCl(OEt)3、GeCl2(OEt)2、GeCl3(OEt)、GeCl(OPrn)3、GeCl2(OPrn))2、GeCl3(OPrn)、GeCl(OPri)3、GeCl2(OPri))2、GeCl3(OPri)、GeCl(OBut)3、GeCl2(OBut))2及GeCl3(OBut),其中OBut係第三丁基烷氧基,OPrn係正丙氧基而且OPri係異丙氧基。此類化合物較佳為熱安定性並且具有防止歧化反應的大型烷氧基。
該等矽烷基碲前驅物可包括選自由下列所組成
的群組的二矽烷基碲、矽烷基烷基碲或矽烷基胺基碲:
在此R1、R2、R3、R4、R5及R6獨立地為氫、C1-C10烷基或C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團。例示性二矽烷基碲前驅物包括,舉例來說,雙(三甲基矽烷基)碲、雙(三乙基矽烷基)碲及雙(第三丁基二甲基矽烷基)碲。
在本發明的其他具體實施例中,含銻或鉍膜可藉由使矽烷基銻或矽烷基鉍化合物與具有式M(NR14R15)3-xLx或M(NR14R15)4-xLx的混合的胺基和鹵基化合物反應製造,其中M係選自由Sb、Bi、Ga、In、Ge、Sn、Pb所組成的群組;L係選自Cl、Br、I或其混合物;x係1、2或3;R14係C1-C10烷基或C3-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團;及R15係選自由氫、C1-C10烷基或C3-C10烯基、C3-C10環狀基團、C3-C10環烯基或C4-C10芳香族基團所組成的群組。
舉例來說,V.N.Khrustalev等人“New Stable Germylenes,Stannylenes and related compounds.8.Amidogermanium(II)and-tin(II)chlorides R2NE14Cl(E14=Ge,R=Et;Sn,R=Me)Revealing New Structural Motifs”,Appl.Organometal.Chem.,2007;21:551-556中有描述適用於本發明的方法之兼具有胺基和鹵基配位子的鍺化合物,在此以引用的方式將其併入本文。此化合物的實例是[GeCl(NMe2)]2。
適用於本發明的方法且具有混合的胺基和鹵基配位子的銻化合物包括Ensinger,U.and A.Schmidt(1984)、"Dialkylaminostibines.Preparation and spectra" Z.Anorg.Allg.Chem.FIELD Full Journal Title:Zeitschrift fuer Anorganische und Allgemeine Chemie 514:137-48;及Ensinger,U.,W.Schwarz,B.Schrutz,K.Sommer and A.Schmidt(1987)"Methoxostibines.Structure and vibrational spectra." Z.Anorg.Allg.Chem.FIELD Full Journal Title:Zeitschrift fur Anorganische und Allgemeine Chemie 544:181-91所揭示者,在引以引用的方式將其全文併入本文。此化合物的實例包括,舉例來說,Cl2SbNMe2(I)、Cl2SbNMeEt(II)、Cl2SbNEt2(III)、ClSb[NMe2]2(IV)、ClSb[NMeEt]2(V)、ClSb[NEt2]2(VI)、Ga(NMe2)2Cl及Ga(NMe2)Cl2。
適用於本發明的方法的銦化合物包括Frey,R.,V.D.Gupta and G.Linti(1996)."Monomeric bis and叁(amides)的indium"622(6):1060-1064;Carmalt,C.J.and S.J.King(2006),"Gallium(III)and indium(III)alkoxides and aryloxides." Coordination Chemistry Reviews 250(5-6):682-709;Carmalt,C.J.(2001),"Amidocompounds of gallium and indium." Coordination Chemistry Reviews 223(1):217-264;Frey,R.,V.D.Gupta and G.Linti(1996),"Monomeric bis and tris(amides)的indium." Monomere bis-und tris(amide)des indiums 622(6):1060-1064;Suh,S.and D.M.Hoffman(2000)所揭示者。"General Synthesis of Homoleptic Indium
Alkoxide Complexes and the Chemical Vapor Deposition of Indium Oxide Films." Journal of the American Chemical Society 122(39):9396-9404。此類化合物的實例包括,舉例來說,[In(OCH2CH2NMe2)3]2、[In(μ-OtBu)(OtBu)2]2、[In(OCMe2Et)2(-OCMe2Et)]2、In[N(tBu)(SiMe3)]3、In(TMP)3(TMP=2,2,6,6-四甲基六氫吡啶基)及In(N(環己基)2)3。
用於本方法的醇類具有下列通式:
在此R係呈線性、分支或環狀形式的帶1至10個碳的烷基或烯基或芳香族基團。舉例來說,R可為C1-C10烷基、C2-C10烯基、C3-C10環烷基、C2-C10環烯基或C4-C10芳香族基團。在特定具體實施例中,較佳為甲醇。
將1.22g(0.01mol)的200篩號銻粉、0.72g(0.03mol)的氫化鋰及40ml的四氫呋喃(THF)置於100ml燒瓶中。配合攪拌,使該混合物迴流4小時。構成銻的黑色粉末均消失並且生成泥土色沉澱物。接著,使該混合物冷卻至-20℃;添加3.3g(0.03mol)的三甲基氯矽烷。讓該混合物暖化至室溫。等到攪拌4小時之後,在惰性氣氛作用下過濾該混合物。該溶劑係藉由蒸餾移除。藉由真空蒸餾將叁(三甲基矽烷基)銻純化。
將1.22g(0.01mol)的200篩號銻粉、0.72g(0.03mol)的氫化鋰及40ml的四氫呋喃(THF)置於100ml燒瓶中。配合攪拌,使該混合物迴流4小時。構成銻的黑色粉末均消失並且生成泥土色沉澱物。接著,使該混合物冷卻至-20℃;添加2.83g(0.03mol)的二甲基氯矽烷。讓該混合物暖化至室溫。等到攪拌4小時之後,在惰性氣氛作用下過濾該混合物。該溶劑係藉由蒸餾移除。藉由真空蒸餾將叁(二甲基矽烷基)銻純化。
將3.65g(0.03mol)的200篩號銻粉、2.07g(0.09mol)的鈉、1.15g(0.009mol)的萘及50ml的THF置於100ml燒瓶中。於室溫下攪拌該混合物24小時。構成銻的黑色粉末和鈉均消失並且生成泥土色沉澱物。接著,使該混合物冷卻至-20℃;添加8.51g(0.09mol)的二甲基氯矽烷。讓該混合物暖化至室溫。等到攪拌4小時之後,在惰性氣氛作用下過濾該混合物。該溶劑係藉由蒸餾移除。藉由真空蒸餾將叁(二甲基矽烷基)銻純化。
6.27g(0.03mol)的200篩號鉍粉、2.07g(0.09mol)的鈉、1.15g(0.009mol)的萘及50ml的THF置於100ml燒瓶中。於室溫下攪拌該混合物24小時。構成銻的黑色粉末
和鈉均消失並且生成泥土色沉澱物。接著,使該混合物冷卻至-20℃;添加9.77g(0.09mol)的三甲基氯矽烷。讓該混合物暖化至室溫。等到攪拌4小時之後,在惰性氣氛作用下過濾該混合物。該溶劑係藉由蒸餾移除。叁(三甲基矽烷基)鉍純化能藉由真空蒸餾。
把0.05g的叁(二甲基矽烷基)銻置於填充氮並且裝上橡膠隔膜的100ml派熱司玻璃(pyrex glass)燒瓶底部。利用注射器緩慢添加0.1g的甲醇。開始有閃亮的黑色膜開始沉積於該燒瓶的玻璃壁內側。經過數分鐘之後,整個燒瓶內部均覆著暗沉的灰/黑色銻膜。
使0.43g(0.001mol)叁(三甲基矽烷基)鉍溶於6ml的乙腈。於室溫下將0.12g四甲氧基鍺烷加於該溶液。反應是放熱性。立即生成黑色沉澱物。將該沉積物過濾出來並且以THF清洗並且於空氣中乾燥。研究該黑色固態沉澱物能使用能量色散X射線分析(EDX)聯合掃描式電子顯微鏡(SEM)。結果指示該黑色固體係鍺和鉍的組合物。鉍化鍺不溶於有機溶劑。
使0.38g(0.001mol)三第三戊氧化銦溶於6ml
的乙腈。於室溫下將0.34g(0.001mol)叁(三甲基矽烷基)銻加於該溶液。反應是放熱性。立即生成黑色沉澱物。將該沉積物過濾出來並且以THF清洗並且於空氣中乾燥。研究該黑色固態沉澱物能使用能量色散X射線分析(EDX)聯合掃描式電子顯微鏡(SEM)。結果指示該黑色固體係銦和銻的組合物。銻化銦不溶於有機溶劑。
使0.34g(0.001mol)三乙氧化鉍溶於6ml的乙腈。於室溫下將0.34g(0.001mol)叁(三甲基矽烷基)銻加於該溶液。反應是放熱性。立即生成黑色沉澱物。將該沉積物過濾出來並且以THF清洗並且於空氣中乾燥。研究該黑色固態沉澱物能使用能量色散X射線分析(EDX)聯合掃描式電子顯微鏡(SEM)。結果指示該黑色固體係銻和鉍的組合物。銻化鉍不溶於有機溶劑。
利用原子層沉積(ALD)技術來沉積GeBi膜,包括下列步驟:a)把待沉積膜的基材裝於ALD反應器;b)以N2沖洗該反應器並且泵抽降至低於1托耳的低壓並且加熱至進行膜沉積的溫度;c)把固定流速的矽烷基鉍化合物蒸氣當作Bi前驅物引進該反應器。使該反應器充滿此蒸氣經歷短暫固定時間
(經常少於5秒),並且接著泵抽降至1托耳,緊接著以N2沖洗;d)把固定流速的烷氧基鍺烷化合物蒸氣當作Ge前驅物引進該反應器。使該反應器充滿此蒸氣經歷短暫固定時間(經常少於5秒),並且接著泵抽降至1托耳,緊接著以N2沖洗;及重複進行步驟c)至d)直到達成該膜的所欲厚度。在另一實例中,能於步驟c)中引進烷氧基鍺烷化合物同時於步驟d)中引進矽烷基鉍化合物。
憑藉著此沉積化學,使基材例如矽、氧化矽、氮化矽、氮化鈦的表面上能沉積高保形性GeBi膜。製程溫度範圍可能從室溫至400℃。
利用原子層沉積(ALD)技術來沉積銻膜,包括下列步驟:a)把待沉積膜的基材裝於ALD反應器;b)以N2沖洗該反應器並且泵抽降至低於1托耳的低壓並且加熱至進行膜沉積的溫度;c)把固定流速的三矽烷基銻化合物蒸氣引進該反應器。使該反應器充滿此蒸氣經歷短暫固定時間(經常少於5秒),並且接著泵抽降至1托耳,緊接著以N2沖洗;d)把固定流速的烷氧基銻化合物蒸氣引進該反應器。使該反應器充滿此蒸氣經歷短暫固定時間(經常少於5秒),
並且接著泵抽降至1托耳,緊接著以N2沖洗;及重複進行步驟c)至d)直到達成該膜的所欲厚度。在另一實例中,能於步驟c)中引進烷氧基鍺烷化合物同時於步驟d)中引進三矽烷基鉍化合物。
憑藉著此沉積化學,使基材例如矽、氧化矽、氮化矽、氮化鈦的表面上能沉積高保形性銻膜。製程溫度範圍可能從室溫至400℃。
利用原子層沉積(ALD)技術來沉積GeBi膜,包括下列步驟:a)把待沉積膜的基材裝於ALD反應器;b)以N2沖洗該反應器並且泵抽降至低於1托耳的低壓並且加熱至進行膜沉積的溫度;c)把固定流速的烷氧基鍺烷化合物蒸氣當作Ge前驅物引進該反應器。使該反應器充滿此蒸氣經歷短暫固定時間(經常少於5秒),並且接著泵抽降至1托耳,緊接著以N2沖洗;及d)把固定流速的二矽烷基碲化合物蒸氣當作Te前驅物引進該反應器。使該反應器充滿此蒸氣經歷短暫固定時間(經常少於5秒),並且接著泵抽降至1托耳,緊接著以N2沖洗;e)把固定流速的烷氧基鍺烷化合物蒸氣Ge前驅物引進該反應器。使該反應器充滿此蒸氣經歷短暫固定時間(經
常少於5秒),並且接著泵抽降至1托耳,緊接著以N2沖洗;f)把固定流速的三矽烷基銻化合物蒸氣當作Sb前驅物引進該反應器。使該反應器充滿此蒸氣經歷短暫固定時間(經常少於5秒),並且接著泵抽降至1托耳,緊接著以N2沖洗;重複進行步驟c)至f)直到達成該膜的所欲厚度。
憑藉著此沉積化學,使基材例如矽、氧化矽、氮化矽、氮化鈦的表面上能沉積高保形性GeSbTe膜。製程溫度範圍可能從室溫至400℃。
利用原子層沉積(ALD)技術來沉積GeBiTe膜,包括下列步驟:a)把待沉積膜的基材裝於ALD反應器;b)以N2沖洗該反應器並且泵抽降至低於1托耳的低壓並且加熱至進行膜沉積的溫度;c)把固定流速的烷氧基鍺烷化合物蒸氣當作Ge前驅物引進該反應器。使該反應器充滿此蒸氣經歷短暫固定時間(經常少於5秒),並且接著泵抽降至1托耳,緊接著以N2沖洗;及d)把固定流速的二矽烷基碲化合物蒸氣當作Te前驅物引進該反應器。使該反應器充滿此蒸氣經歷短暫固定時間(經常少於5秒),並且接著泵抽降至1托耳,緊接著以
N2沖洗;e)把固定流速的烷氧基鍺烷化合物蒸氣Ge前驅物引進該反應器。使該反應器充滿此蒸氣經歷短暫固定時間(經常少於5秒),並且接著泵抽降至1托耳,緊接著以N2沖洗;f)把固定流速的三矽烷基鉍化合物蒸氣當作Bi前驅物引進該反應器。使該反應器充滿此蒸氣經歷短暫固定時間(經常少於5秒),並且接著泵抽降至1托耳,緊接著以N2沖洗;重複進行步驟c)至f)直到達成該膜的所欲厚度。
憑藉著此沉積化學,使基材例如矽、氧化矽、氮化矽、氮化鈦的表面上能沉積高保形性GeSbTe膜。製程溫度範圍可能從室溫至400℃。
Claims (20)
- 一種用於將含銻膜製造於基材表面上之ALD方法,該方法包含下列步驟:把烷氧化鍺當作前驅物引進沉積艙,其中該烷氧化鍺係由式Ge(OR14)4來表示,其中R14係C1-C10烷基、C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團,以形成烷氧化鍺的分子層於該基材表面上;及把選自由下列所組成的群組之矽烷基銻前驅物引進該沉積艙:
- 如申請專利範圍第1項之方法,其中該矽烷基銻前驅物係選自由叁(三甲基矽烷基)銻、叁(三乙基矽烷基)銻、叁(第三丁 基二甲基矽烷基)銻及叁(二甲基矽烷基)銻所組成的群組。
- 如申請專利範圍第1項之方法,其中依序重複進行這些步驟。
- 如申請專利範圍第1項之方法,其中該沉積艙的溫度係介於室溫至400℃。
- 一種用於將鍺-鉍-碲合金膜製造於基材表面上之ALD方法,該方法包含下列步驟:把烷氧化鍺當作前驅物引進沉積艙,其中該烷氧化鍺係由式Ge(OR14)4來表示,其中R14係C1-C10烷基、C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團,以形成烷氧化鍺的分子層於該基材表面上;及把選自由下列所組成的群組之碲前驅物引進該沉積艙:
- 如申請專利範圍第5項之方法,其中該矽烷基鉍前驅物係選自由叁(三甲基矽烷基)鉍、叁(三乙基矽烷基)鉍、叁(第三丁基二甲基矽烷基)鉍及叁(二甲基矽烷基)鉍所組成的群組。
- 如申請專利範圍第5項之方法,其中依序重複進行這些步驟。
- 如申請專利範圍第5項之方法,其中該沉積艙的溫度係從室溫至400℃。
- 如申請專利範圍第5項之方法,其中該醇係甲醇。
- 一種用於將含銻-或鉍-膜製造於基材表面上之ALD方法,該方法包含下列步驟:把選自由下列所組成的群組之矽烷基銻或鉍前驅物引進沉積艙:
- 如申請專利範圍第10項之方法,其中該矽烷基銻前驅物係選自由叁(三甲基矽烷基)銻、叁(三乙基矽烷基)銻、叁(第三丁基二甲基矽烷基)銻及叁(二甲基矽烷基)銻所組成的群組。
- 如申請專利範圍第10項之方法,其中該矽烷基鉍前驅物係叁(三甲基矽烷基)鉍。
- 如申請專利範圍第10項之方法,其中依序重複進行這些步驟。
- 如申請專利範圍第10項之方法,其中該沉積艙的溫度係從室溫至400℃。
- 如申請專利範圍第10項之方法,其中該第二前驅物係選自由SbCl(OMe)2、SbCl2(OMe)、SbBr(OMe)2、SbBr2(OMe)、SbI(OMe)2、SbCl(OEt)2、SbCl2(OEt)、SbCl(OPri)2、SbCl2(OPri)、BiCl(OMe)2、BiCl2(OMe)、BiCl(OEt)2、BiCl2(OEt)、BiCl(OPri)2、BiCl2(OPri)、Cl2SbNMeEt(II)、Cl2SbNEt2(III)、ClSb[NMe2]2(IV)、ClSb[NMeEt]2(V)、ClSb[NEt2]2(VI)、Ga(NMe2)2Cl、Ga(NMe2)Cl2、[In(OCH2CH2NMe2)3]2、[In(μ-OtBu)(OtBu)2]2、[In(OCMe2Et)2(m-OCMe2Et)]2、In[N(tBu)(SiMe3)]3、In(TMP)3(TMP=2,2,6,6-四甲基六氫吡啶基)及In(N(環己基)2)3所組成的群組。
- 一種用於將鍺-銻-碲(GST)膜或鍺-鉍-碲(GBT)膜製造於基材表面上之ALD方法,該方法包含下列步驟:把選自Ge(OR14)4-xLx的鍺前驅物引進沉積艙,其中L係選 自Cl、Br、I及其混合物;x係0、1、2或3;R14係C1-C10烷基、C2-C10烯基、C3-C10環烷基、C3-C10環烯基或C4-C10芳香族基團;引進該沉積艙一矽烷基碲前驅物,該矽烷基碲前驅物包括選自由下列所組成的群組之二矽烷基碲、矽烷基烷基碲或矽烷基胺基碲:
- 如申請專利範圍第16項之方法,其中該鍺前驅物係選自由Ge(OMe)4、Ge(OEt)4、Ge(OPrn)4、Ge(OPri)4、GeCl(OMe)3、GeCl2(OMe)2、GeCl3(OMe)、GeCl(OEt)3、GeCl2(OEt)2、GeCl3(OEt)、GeCl(OPrn)3、GeCl(OPrn)3、GeCl2(OPrn))2、GeCl2(OPri)2、GeCl3(OPri)、GeCl(OBut)3、GeCl2(OBut))2及GeCl3(OBut)所組成的群組。
- 如申請專利範圍第16項之方法,其中該矽烷基銻前驅物係選自由叁(三甲基矽烷基)銻、叁(三乙基矽烷基)銻、叁(第三丁基二甲基矽烷基)銻及叁(二甲基矽烷基)銻所組成的群組。
- 如申請專利範圍第16項之方法,其中該矽烷基鉍前驅物係選自由叁(三甲基矽烷基)鉍、叁(三乙基矽烷基)鉍及叁(第三丁基二甲基矽烷基)鉍所組成的群組。
- 如申請專利範圍第16項之方法,其中該二矽烷基碲前驅物係選自由雙(三甲基矽烷基)碲、雙(三乙基矽烷基)碲及雙(第三丁基二甲基矽烷基)碲所組成的群組。
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2016
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JP2014037411A (ja) | 2014-02-27 |
JP2016084544A (ja) | 2016-05-19 |
KR20160018639A (ko) | 2016-02-17 |
JP5905858B2 (ja) | 2016-04-20 |
KR20140021979A (ko) | 2014-02-21 |
KR102050306B1 (ko) | 2019-11-29 |
EP2698373A2 (en) | 2014-02-19 |
CN103590017A (zh) | 2014-02-19 |
EP3293193A2 (en) | 2018-03-14 |
KR20190099188A (ko) | 2019-08-26 |
KR102084520B1 (ko) | 2020-03-04 |
JP6251300B2 (ja) | 2017-12-20 |
EP2698373A3 (en) | 2014-04-09 |
KR102204999B1 (ko) | 2021-01-18 |
TWI529258B (zh) | 2016-04-11 |
CN103590017B (zh) | 2016-08-17 |
EP2698373B1 (en) | 2018-09-19 |
EP3293193A3 (en) | 2018-05-16 |
KR20160039167A (ko) | 2016-04-08 |
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