TWI615497B - 金屬胺化物沉積前驅物及具有惰性安瓿襯裡之該前驅物的穩定化 - Google Patents
金屬胺化物沉積前驅物及具有惰性安瓿襯裡之該前驅物的穩定化 Download PDFInfo
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- TWI615497B TWI615497B TW103104427A TW103104427A TWI615497B TW I615497 B TWI615497 B TW I615497B TW 103104427 A TW103104427 A TW 103104427A TW 103104427 A TW103104427 A TW 103104427A TW I615497 B TWI615497 B TW I615497B
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- Prior art keywords
- precursor
- gas
- manganese
- substrate
- metal oxide
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Links
- 239000002243 precursor Substances 0.000 title claims abstract description 134
- 150000001408 amides Chemical class 0.000 title claims description 4
- 230000006641 stabilisation Effects 0.000 title abstract description 3
- 238000011105 stabilization Methods 0.000 title abstract description 3
- 230000008021 deposition Effects 0.000 title description 21
- 239000003708 ampul Substances 0.000 title description 17
- 229910052751 metal Inorganic materials 0.000 title description 9
- 239000002184 metal Substances 0.000 title description 9
- 238000000034 method Methods 0.000 claims abstract description 68
- 239000011572 manganese Substances 0.000 claims abstract description 51
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003446 ligand Substances 0.000 claims abstract description 35
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims description 67
- 239000007789 gas Substances 0.000 claims description 58
- 238000000151 deposition Methods 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims description 22
- 150000004706 metal oxides Chemical class 0.000 claims description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 14
- 229910018648 Mn—N Inorganic materials 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012707 chemical precursor Substances 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 150000001345 alkine derivatives Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 150000003512 tertiary amines Chemical class 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- ZKEYULQFFYBZBG-UHFFFAOYSA-N lanthanum carbide Chemical compound [La].[C-]#[C] ZKEYULQFFYBZBG-UHFFFAOYSA-N 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- JEROREPODAPBAY-UHFFFAOYSA-N [La].ClOCl Chemical compound [La].ClOCl JEROREPODAPBAY-UHFFFAOYSA-N 0.000 claims description 2
- UJKVCWLHRXLAAK-UHFFFAOYSA-N O(O)O.[La] Chemical compound O(O)O.[La] UJKVCWLHRXLAAK-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000012545 processing Methods 0.000 description 34
- 239000000463 material Substances 0.000 description 33
- 230000008569 process Effects 0.000 description 29
- 239000010408 film Substances 0.000 description 20
- 210000002381 plasma Anatomy 0.000 description 20
- 238000000231 atomic layer deposition Methods 0.000 description 18
- 239000012159 carrier gas Substances 0.000 description 15
- 238000012546 transfer Methods 0.000 description 13
- 239000003921 oil Substances 0.000 description 11
- 238000005229 chemical vapour deposition Methods 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 238000005137 deposition process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 230000000087 stabilizing effect Effects 0.000 description 6
- 230000008016 vaporization Effects 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- 238000001757 thermogravimetry curve Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OPICPBLVZCCONG-UHFFFAOYSA-N [Ta].[C]=O Chemical compound [Ta].[C]=O OPICPBLVZCCONG-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 4
- 229910003468 tantalcarbide Inorganic materials 0.000 description 4
- 238000000427 thin-film deposition Methods 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- RRZKHZBOZDIQJG-UHFFFAOYSA-N azane;manganese Chemical compound N.[Mn] RRZKHZBOZDIQJG-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000012697 Mn precursor Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- WYEMLYFITZORAB-UHFFFAOYSA-N boscalid Chemical compound C1=CC(Cl)=CC=C1C1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl WYEMLYFITZORAB-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- -1 manganese sulfonium alkyl amide Chemical class 0.000 description 2
- 239000013212 metal-organic material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 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 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- TUTXBKLGUMBWGR-UHFFFAOYSA-N CC(CCCCCCCCCN(CCCCCCCCCC)CCCCCCCCCC(C)(C)C)(C)C Chemical compound CC(CCCCCCCCCN(CCCCCCCCCC)CCCCCCCCCC(C)(C)C)(C)C TUTXBKLGUMBWGR-UHFFFAOYSA-N 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical group C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- NESWUFFSSGAALZ-UHFFFAOYSA-N N-decyl-10,10-dimethylundecan-1-amine Chemical compound CC(CCCCCCCCCNCCCCCCCCCC)(C)C NESWUFFSSGAALZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 238000013019 agitation Methods 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
- 239000012080 ambient air Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 229940097206 manganese citrate Drugs 0.000 description 1
- 235000014872 manganese citrate Nutrition 0.000 description 1
- 239000011564 manganese citrate 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
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005019 vapor deposition process Methods 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
Classifications
-
- 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
-
- 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
- C23C16/34—Nitrides
-
- 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
- C23C16/448—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4481—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material
-
- 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]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45536—Use of plasma, radiation or electromagnetic fields
-
- 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
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Abstract
本文所描述的為用於前驅物之穩定化的方法及設備,該等方法及設備可用於沉積含錳薄膜。某些方法及設備係關於經添加襯裡之安瓿及/或2-電子供體配位子。
Description
本發明之實施例一般而言係關於薄膜沉積。更特定言之,本發明之實施例係關於薄膜沉積製程期間前驅物的穩定化。
積體電路已發展為在單一晶片上可包括數百萬之電晶體、電容器及電阻器之複雜裝置。晶片設計之發展不斷要求更快的電路及更大的電路密度,更快的電路及更大的電路密度要求越來越精確之製造製程。基板之精確處理要求對在處理期間所使用的流體之傳遞中的溫度、速率及壓力的精確控制。
化學氣相沈積(CVD)及原子層沉積(ALD)為用於在基板上形成或沉積多種材料之兩種沉積製程。一般而言,CVD及ALD製程涉及將氣態反應物遞送至基板表面,在有利於該反應之熱力學的溫度及壓力條件下,在該基板表面
處發生化學反應。
許多該等沉積製程使用加熱容器或罐(諸如安瓿或起泡器),該加熱容器或罐在有助於汽化該前驅物的條件下含有揮發性液態前驅物。儘管如此,薄膜之沉積的共有問題為在安瓿內,許多前驅物具有有限的穩定性。尤其是在具有低配位數之金屬前驅物的情況下如此,因為金屬中心更易受與其他化合物反應之攻擊。該錯合物可與雜質、分解產物或甚至安瓿本身之金屬表面反應。在不增加前驅物之穩定性的情況下,沉積工具之產量減少,或更糟的是,可能需要完全重新設計製程條件,以抑制分解及/不良反應。因此,需要用於穩定金屬前驅物之額外的設備及方法。
本發明之一個態樣係關於一種用於生成化學前驅物氣體之設備。該設備包含:罐,該罐具有形成內部體積之側壁、頂端及底部;進氣埠及出氣埠,該進氣埠及出氣埠與內部體積形成流體連通;襯裡,該襯裡位於該側壁、頂端或底部之至少部分上,其中該襯裡包含惰性金屬氧化物;以及前驅物,該前驅物位於該罐之內部體積中,其中該前驅物包含至少一個Mn-N鍵及2-電子供體配位子。在一或更多實施例中,該襯裡位於底部之至少一部分上。在一些實施例中,該惰性金屬氧化物包含一介電質。在一或更多實施例中,該惰性金屬氧化物包含SiO2、Al2O3、TiO2、碳化矽、碳氧化矽或Ta2O5。在一些實施例中,2-電子供體配位子包含吡啶、四氫呋喃或四氫噻吩、四甲基乙二胺、乙腈、三級胺或2,2’-聯吡
啶。在一或更多實施例中,該前驅物具有一結構,該結構表示為:
本發明之另一態樣係關於一種沉積含錳薄膜之方法。該方法包含以下步驟:提供含有至少一個Mn-N鍵之前驅物;以及使該前驅物流動穿過用於生成化學前驅物氣體之設備,其中該設備具有包含惰性金屬氧化物之襯裡。在一或更多實施例中,該惰性金屬氧化物包含一介電質。在一些實施例中,該惰性金屬氧化物包含SiO2、Al2O3、TiO2、碳化矽、碳氧化矽或Ta2O5。在一或更多實施例中,該前驅物具有一結構,該結構表示為:
其中各A獨立地選自於碳或矽,且各R獨立地選自於氫、甲基、取代或非取代烷烴、支鏈或非支鏈烷烴、取代或非取代烯烴、支鏈或非支鏈烯烴、取代或非取代炔烴、支鏈或非支鏈炔烴或取代或非取代芳族物。
在一或更多實施例中,各A為矽。在一些實施例中,各R基為甲基。在一或更多實施例中,前驅物包含雙(雙三甲基矽烷基)醯胺錳。在一些實施例中,該方法進一步包含以下步驟:將基板表面曝露於該雙(雙三甲基矽烷基)醯胺錳及包含NH3之第二前驅物。在一或更多實施例中,該前驅物進一步含有2-電子供體配位子。在一些實施例中,2-電子供體配位子包含吡啶、四氫呋喃或四氫噻吩、四甲基乙二胺、乙腈、三級胺或2,2’-聯吡啶。在一或更多實施例中,至少Mn-N鍵為該2-電子供體配位子之部分。在一些實施例中,該前驅物具有一結構,該結構表示為:
在一或更多實施例中,該方法進一步包含將基板表面曝露於該前驅物。
300‧‧‧來源罐
302‧‧‧載氣源
306‧‧‧處理腔室
312‧‧‧閥
314‧‧‧閥
402‧‧‧圓筒形側壁
404‧‧‧蓋
406‧‧‧進氣埠
408‧‧‧出氣埠
410‧‧‧擋板
414‧‧‧前驅物材料
416‧‧‧液體
418‧‧‧上部區域
420‧‧‧外殼
422‧‧‧進氣管
424‧‧‧第一端
426‧‧‧第二端
430‧‧‧電阻加熱器
432‧‧‧底部
436A‧‧‧斷開配件
436B‧‧‧斷開配件
438‧‧‧內部體積
444‧‧‧襯裡
450‧‧‧集油器
452‧‧‧集油器主體
454‧‧‧擋板
456‧‧‧中心線
因此,參照實施例來提供於上文簡要概述的本發明的更詳細敘述,以達到且更詳細瞭解本發明的上述的特徵結構,其中一部分實施例在附圖中圖示。然而應注意,附圖僅圖示本發明之典型實施例,且因為本發明承認其他同等有效之實施例,所以該等圖式並不欲視為本發明之範疇的限制。
第1圖為根據本發明之一或更多實施例之設備的一個示例性實施例之截面側視圖;第2圖為圖表,該圖表圖示根據本發明之一或更多實施例之一對照實例及三個實例的非揮發性殘留物之百分比;第3圖為圖表,該圖表圖示根據本發明之一或更多實施例之一對照實例及三個實例的非揮發性殘留物之百分比;第4圖為Mn(TMSA)2之熱解重量曲線;第5圖為Mn(TMSA)2(py)2之熱解重量曲線;以及第6圖為Mn(TMSA)2(TMEDA)之熱解重量曲線。
在描述本發明之若干示例性實施例之前,應瞭解,本發明不受以下描述所闡述的構造或製程步驟之詳細內容限制。本發明能夠包括其他實施例,且能夠以多種方式實踐或實施本發明。
已發現,藉由修改配位子及/或修改在薄膜沉積製程期間使用的裝置,可穩定化Mn前驅物。如以上所論述,前驅物可與安瓿之內壁反應,該安瓿之內壁可由例如不銹鋼製成。儘管如此,使用惰性金屬氧化物為安瓿之內壁添加襯裡,可助於防止前驅物之反應。另外,該前驅物可經合成,以便該前驅物經配位為亦含有2-電子供體部分之醯胺配位子,或可添加獨立的2-電子供體配位子,從而提供化學穩定性。本文所描述之設備及製程助於穩定化金屬有機物(亦即前驅物),該金屬有機物在高溫下可經受降解。
因此,本發明之態樣提供增強之穩定性,該增強之穩定性防止前驅物在生產運行期間降解。前驅物穩定性的增大意謂沉積工具的產量可增加,同時完全避免必須重新設計製程條件。
設備
本發明之一態樣係關於一種用於生成化學前驅物氣體之設備,在一些實施例中,該設備被稱為安瓿。該設備包含:罐,該罐具有形成內部體積之側壁、頂端及底部;進氣埠及出氣埠,該進氣埠及出氣埠與內部體積形成流體連通;襯裡,該襯裡位於該側壁、頂端或底部之至少部分上,其中該襯裡包含惰性金屬氧化物;以及前驅物,該前驅物位於該
罐之內部體積中,其中該前驅物包含至少一個Mn-N鍵及2-電子供體配位子。在一或更多實施例中,該襯裡位於底部之至少部分上。在一些實施例中,該設備為含有金屬有機物之機載貯器(on-board reservoir)。在一或更多實施例中,該設備含有加熱元件,以加熱該等前驅物。
該設備之變體包括不同的襯裡材料。例如,在一些實施例中,該惰性金屬氧化物包含介電質。在其他實施例中,該惰性金屬氧化物包含SiO2、Al2O3、TiO2、碳化矽、碳氧化矽或Ta2O5。在一或更多實施例中,該惰性金屬氧化物為矽基(silicon-based)惰性金屬氧化物。
在一些實施例中,該2-電子供體配位子為助於穩定化該前驅物之配位子。在一些實施例中,Mn-N鍵為該2-電子供體配位子之一部分。在一或更多實施例中,該2-電子供體配位子包含吡啶(py)、四氫呋喃(THF)、四氫噻吩、四甲基乙二胺(TMEDA)配位子、乙腈、三級胺或2,2’-聯吡啶。在一些實施例中,該前驅物含有三甲基矽烷基醯胺(TMSA)配位子。在其他實施例中,該前驅物具有一結構,該結構表示為:
根據Horvath等人所著的「Manganese(II)silylamides」(「Manganese(II)silylamides」特定地描述了Mn(TMSA)2(THF)之合成)中所述之方法可合成本文所描述之穩定化前驅物。THF中之MnCl2及LiN(SiMe3)2用於生產該前驅物。該製程可適用於其他配位子及使用並行製程。
可有利地為安瓿添加襯裡,因為該安瓿之內表面可在很長一段時間內保持與沉積化學物接觸。因此,在一或更多實施例中,僅為沉積腔室系統之安瓿添加襯裡。儘管閥及接線可能不與沉積化學物有長時間之接觸,但在本發明之一或更多實施例中,彼等閥及接線亦可被塗覆。
第1圖圖示該等設備之一實施例之剖視圖,或者該等設備被稱為「來源罐」300。「來源罐」300通常耦接在載氣源302與處理腔室306之間。來源罐300通常包含安瓿或其他具有外殼420之密封容器,該安瓿或其他密封容器適用於儲存前驅物材料414(例如Mn(TMSA)2(py)2),前驅物材料414經由昇華或汽化製程可生成製程(或其他)氣體。前驅物材料414包含一前驅物,該前驅物含有至少一個Mn-N鍵及2-電子供體配位子。外殼420通常由實質上對前驅物材料414及自前驅物材料生成之氣體為惰性的材料製成,且因此,構造之材料可基於欲生成之氣體變化。
外殼420可具有任何數目之幾何形狀。在第1圖圖示之實施例中,外殼420包含圓筒形側壁402及底部432,該圓筒形側壁402及該底部432由蓋404密封。藉由焊接、接合、黏著劑或其他密封方法可將蓋404耦接至側壁402。或
者,側壁402與蓋404之間的接合處可安置密封件、O形環、密合墊片或類似物,以防止自來源罐300滲漏。側壁402或者可包含其他中空幾何形狀,例如中空方管。
根據本發明之一或更多實施例,第1圖之設備亦具有沿底部432之襯裡444。該襯裡可包含介電質,或在其他實施例中包含SiO2、Al2O3、TiO2、碳化矽、碳氧化矽或Ta2O5。
進氣埠406及出氣埠408形成為穿過該來源罐,以允許氣體流入或流出來源罐300。埠406、408可形成為穿過來源罐300之蓋404及/或側壁402。埠406、408通常為可密封的,以在將來源罐300從該氣體遞送系統(未圖示)移除期間,允許來源罐300之內部與周圍環境隔離。在一實施例中,閥312、314密封地耦接至埠406、408,以在為再充裝前驅物材料414或置換來源罐300而將來源罐300從該氣體遞送系統移除時,防止自來源罐300滲漏。配對斷開配件436A、436B可耦接至閥312、314,以促進從氣體遞送系統304移除來源罐300,及將來源罐300置換至氣體分配系統304。閥312、314通常為球形閥或其他可靠密封閥,該等閥允許將來源罐300從有效地加載及再循環的該系統移除,同時在填充、傳輸或耦接來源罐300至該氣體遞送系統期間,最小化自來源罐300之潛在滲漏。或者,經由再填充埠(未圖示)對來源罐300進行再填充,該再填充埠諸如具有VCR配件的小管,該再填充埠安置於來源罐300之蓋404上。藉由移除蓋404或經由埠406、408之一者可將前驅物材料414引入來源罐300。
來源罐300可包括至少一個擋板410,擋板410安置於來源罐300之上部區域418之內部。擋板410安置於進氣埠406與出氣埠408之間,形成延長的平均流道,進而防止載氣自進氣埠406至出氣埠408的直接(亦即直線)流動。此具有增加載氣在來源罐300中的平均停留時間,及增加由載氣所載運的昇華或汽化前驅物氣體之數量的效應。此外,擋板410將載氣導引在安置於來源罐300中之前驅物材料414之整體曝露表面上,以確保可重複的氣體生成特徵及對前驅物材料414之有效的消耗。擋板410之數目、間隔及形狀可經選擇以調諧來源罐300,以用於前驅物氣體的最佳生成。舉例而言,更多數目之擋板410可經選擇以在前驅物材料414處賦予較高的載氣速度,或擋板410之形狀可經配置以控制前驅物材料414之消耗,以更有效地使用該前驅物材料。
視情況,進氣管422可安置於來源罐300之內部體積438中。管422藉由第一端424耦接至來源罐300之進氣埠406,且在來源罐300之上部區域418中第二端426處終止。
視情況,該設備可含有集油器450,因為前驅物材料414之攪動可能引發液滴被夾帶於載氣中且載運至處理腔室306。為防止液體416之液滴到達處理腔室306,集油器450可視情況耦接至來源罐300之出口埠408。集油器450可包括主體452,主體452包含複數個交錯的擋板454,該等複數個擋板454延伸超過集油器主體452之中心線456,且朝向來源罐300至少輕微地向下傾斜。擋板454迫使氣體流向處理腔室306,以圍繞擋板454沿曲折路徑流動。擋板454之表面區
域提供曝露於流動氣體之較大的表面區域,該表面區域黏附有可能夾帶於氣體中之油液滴。擋板454之向下傾斜允許積聚於集油器中之任何油向下流動,且回流至來源罐300。
在預定的溫度和壓力下,前驅物材料414生成前驅物氣體。自前驅物材料414昇華或汽化之氣體可在來源罐300之上部區域418中積聚,且該氣體可藉由惰性載氣清除,該惰性氣體經由進氣埠406進入且自出氣埠408流出,以經載運到達處理腔室306。在一實施例中,藉由安置於側壁402附近之電阻加熱器430將前驅物材料414加熱至一預定溫度。或者,可藉由其他方式加熱前驅物材料414,諸如藉由安置於來源罐300之上部區域418或下部區域434中之匣式加熱器(未圖示),或藉由使用置放於載氣進氣埠406之上游的加熱器(未圖示)預加熱載氣。
沉積製程
在沉積含錳薄膜期間可使用本文所描述之設備。因此,本發明之一態樣係關於一種使用本文所描述的用於生成化學前驅物氣體之任何設備沉積含錳薄膜之方法。包含在該設備內部之前驅物在薄膜沉積製程中可用作錳源。一或更多實施例係關於在本文所描述的用於生成化學前驅物氣體之設備中汽化本文所描述之前驅物。隨後可將基板表面曝露於該汽化前驅物。在一或更多實施例中,2-電子供體配位子包含吡啶(py)、四氫呋喃(THF)、四氫噻吩或四甲基乙二胺(TMEDA)配位子。在其他實施例中,該前驅物具有一結構,該結構表示為:
本發明之另一態樣係關於一種沉積含錳薄膜之方法,該方法包含以下步驟:提供包含至少一個Mn-N鍵之前驅物;以及使該前驅物流動穿過安瓿,該安瓿具有包含惰性金屬氧化物之襯裡。該方法可為使用用於生成化學前驅物氣體之安瓿或其他設備之任何沉積製程之部分。因此例如,該方法可為化學氣相沉積(CVD)、原子層沉積(ALD)、電漿增強化學氣相沉積(PECVD)、電漿增強原子層沉積(PEALD)或其他沉積製程之部分。本文所描述之製程可用於沉積多種含錳薄膜,包括但不限於MnN及基本上由錳構成之薄膜。因此,在一或更多實施例中,該方法進一步包含將基板表面曝露於本文所描述之任何前驅物。
以上描述之設備的任何變體亦可應用於該方法。因此,例如,在一或更多實施例中,惰性金屬氧化物包含介電質。在其他實施例中,該惰性金屬氧化物包含SiO2、Al2O3、TiO2、碳化矽、碳氧化矽或Ta2O5。
如上所述,前驅物包含至少一個Mn-N鍵。在一或更多實施例中,該前驅物為任意一種如上所述之穩定化前驅物。亦即,在一些實施例中,該前驅物進一步包含2-電子供
體配位子,該2-電子供體配位子自身可能含有Mn-N鍵。在一或更多實施例中,2-電子供體配位子為有助於穩定化該前驅物之配位子。在一些實施例中,2-電子供體配位子包含吡啶(py)、四氫呋喃(THF)、四氫噻吩或四甲基乙二胺(TMEDA)配位子。在其他實施例中,該前驅物具有一結構,該結構表示為:
在一些實施例中,該前驅物具有一結構,該結構表示為:
其中各A獨立地選自於碳或矽,且各R獨立地選自於氫、甲基、取代或非取代烷烴、支鏈或非支鏈烷烴、取代或非取代烯烴、支鏈或非支鏈烯烴、取代或非取代炔烴、支鏈或非支鏈炔烴或取代或非取代芳族物。錳之氧化態可為能夠與基板或第二前驅物反應之任何適當的氧化態。在一些實施例中,錳為Mn(II)或Mn(III)。在一或更多實施例中,各A為矽。在
一些實施例中,各R基為甲基。在其他實施例中,該前驅物包含雙(雙三甲基矽烷基)醯胺錳,該雙(雙三甲基矽烷基)醯胺錳具有一結構,該結構表示為:
以上前驅物可用於自有機金屬前驅物生成錳(Mn)或氮化錳(MnNx)。該等沉積方法可為原子層沉積(ALD)或化學氣相沉積(CVD)。該有機金屬前驅物可包括錳矽烷基醯胺基錯合物。沉積之錳或MnNx薄膜可用作後端製程銅互連中之替代擴散阻障層,以替代當前使用的PVD TaN或ALD TaN。該沉積方法可與ALD TaN沉積整合,以生成摻雜錳之TaN或摻雜有MnNx的鉭。亦可使用其他摻雜劑。在一或更多實施例中,基於錳層之重量,阻障層包含0.1%至10%之摻雜劑。在一些實施例中,阻障層包含0.2重量%至8重量%之摻雜劑。在特定實施例中,阻障層包含0.5重量%至5重量%之摻雜劑。
在一些實施例中,該基板曝露於第一前驅物及第二前驅物。因此,在一或更多實施例中,該方法進一步包含將基板表面曝露於雙(雙三甲基矽烷基)醯胺錳及包含NH3之第二前驅物之步驟。曝露於此等前驅物可實質上同時進行(如
在CVD反應中),或順序地進行(如在ALD反應中)。如在此說明書及附加申請專利範圍中所使用,術語「實質上同時地」意謂兩種前驅物氣體至少部分地共同流入腔室中(以與彼此反應),且共同流向基板表面。熟習此項技術者將瞭解基板之某些區域可能僅簡單地曝露於一種前驅物,直至另一種前驅物擴散至同一區域。
在一些實施例中,Mn前驅物可能與一或更多額外前驅物一起使用。實例包括氨或氫。因此,作為實例,若使用氨,則可形成氮化錳薄膜。反之,若將氫用作第二前驅物,則可能形成基本上由錳構成之薄膜。
在一些實施例中,錳薄膜包含MnNx。一些實施例之x在約0.1至約3之範圍內,或在約0.2至約2之範圍內,或在約0.25至約1之範圍內。在一些實施例中,該薄膜包含矽酸錳,且該薄膜可形成於介電層之上。在一或更多實施例中,當錳薄膜經沉積接近介電質表面時,該錳薄膜包含矽酸錳,而當該錳薄膜經沉積遠離該表面時,該錳薄膜包含氮化錳。從矽酸鹽至氮化物之過渡可為漸進的或以離散步驟進行。
根據本發明之多種實施例,該薄膜實質上可沉積於任何基板材料之上。如本文所使用之「基板表面」代表形成於基板之上的任何基板或材料表面,在製造製程期間於該基板或材料表面上執行薄膜處理。舉例而言,基板表面(可在該基板表面上執行處理)視應用而定包括以下材料:諸如矽、氧化矽、應變矽、絕緣體上矽(SOI)、摻雜碳之氧化矽、氮化矽、經摻雜之矽、鍺、砷化鎵、玻璃、藍寶石及任何其他
材料(諸如金屬、金屬氮化物、金屬合金及其他導電材料)。基板表面上之阻障層、金屬或金屬氮化物包括鈦、氮化鈦、氮化鎢、鉭及氮化鉭、鋁、銅或用於裝置製造之任何其他導體或導電或非導電阻障層。基板可具有多種尺寸,諸如200mm或300mm直徑的晶圓以及矩形或方形之窗格(pane)。基板(在該等基板上可適用本發明之實施例)包括但不限於半導體晶圓(諸如晶態矽(例如Si<100>或Si<111>)、氧化矽、應變矽、矽鍺、摻雜或非摻雜之多晶矽、摻雜或非摻雜之矽晶圓)、III-V族材料(諸如GaAs、GaN、InP等)及圖案化或非圖案化之晶圓。基板可曝露於預處理製程,以拋光、蝕刻、減少、氧化、羥化、退火及/或烘烤該基板表面。
由於本發明之實施例提供一種用於沉積或形成摻雜之含錳薄膜的方法,處理腔室經設置以在氣相沉積製程期間將該基板曝露於一連串氣體及/或電漿。處理腔室將包括反應物之獨立供應器,及任何載氣、淨化氣體及惰性氣體(諸如氬氣及氮氣)之供應器,該等供應器與用於各反應物及氣體之氣體入口流體連通。各入口可藉由適當的流量控制器(諸如質量流量控制器或容積流量控制器)控制,該流量控制器與中央處理單元(CPU)進行通訊,以允許各反應物流至基板,以執行如本文所描述之沉積製程。中央處理單元可為一種可在工業設置中用於控制多個腔室及子處理器的任何形式之電腦處理器。CPU可耦接至記憶體,且CPU可為一或更多易於獲得記憶體,諸如隨機存取記憶體(RAM)、唯讀記憶體(ROM)、快閃記憶體、壓縮碟、軟碟、硬碟或任何其他形
式之本端或遠端數位儲存器。支援電路可耦接至CPU,以用習知方式支持CPU。此等電路包括快取記憶體、電源、時脈電路、輸入/輸出電路系統、子系統及類似電路。
共反應物通常為蒸汽或氣體形式。反應物可使用載氣傳送。載氣、淨化氣體、沉積氣體或其他製程氣體可含有氮氣、氫氣、氬氣、氖氣、氦氣或以上各者之組合。本文所描述之多種電漿(諸如氮電漿或惰性氣體電漿)可自電漿共反應物氣體點燃及/或可包含電漿共反應物氣體。
在一或更多實施例中,用於該製程之多種氣體可自多個孔或出口經脈衝傳遞入口,穿過氣體通道且進入中央通道。在一或更多實施例中,沉積氣體可順序地經脈衝傳遞至噴淋頭,且穿過該噴淋頭。或者,該等氣體可同時流動穿過氣體供應噴嘴或頭,且該基板及/或氣體供應頭可移動,以便將該基板順序地曝露於該等氣體。
在一些實施例中,一或更多層可在電漿增強原子層沉積(PEALD)製程期間形成。在一些製程中,使用電漿提供充足的能量,以促進物質達到激發態,在激發態下表面反應變為有利的或合適的。將電漿引入製程可為連續的或經脈衝的。在一些實施例中,前驅物(或反應氣體)及電漿之順序脈衝被用於處理一層。在一些實施例中,試劑可經本端(亦即,在處理區域內部)離子化或遠端(亦即,在處理區域外部)離子化。在一些實施例中,遠端離子化可發生在沉積腔室之上游,以使得離子或其他高能或發光物質不與沉積薄膜直接接觸。在一些PEALD製程中,電漿自處理腔室之外部生
成,諸如藉由遠端電漿產生器系統。可經由任何為熟習此項技術者所熟知的適當電漿生成製程或技術生成電漿。舉例而言,電漿可藉由微波(MW)頻率產生器或射頻(RF)產生器中的一或更多者生成。視正使用之特定反應物質而定,該電漿之頻率可經調諧。適當之頻率包括但不限於2MHz、13.56MHz、40MHz、60MHz及100MHz。儘管在本文所揭示之沉積製程期間可使用電漿,但應注意,亦可能不需要該等電漿。
根據一或更多實施例,基板在形成層之前及/或之後經受處理。此處理可在同一腔室或一或更多獨立處理腔室中執行。在一些實施例中,將該基板自第一腔室移動至獨立的第二腔室,以進行進一步處理。該基板可直接自第一腔室移動至獨立處理腔室,或該基板可自第一腔室移動至一或更多移送室,且隨後移動至所要的獨立處理腔室。因此,處理設備可包含與移送站連通之多個腔室。可將此類設備稱為「群集工具」或「群集系統」及類似物。
一般而言,群集工具為包含多個腔室之模組化系統,該等腔室執行多種功能,該等功能包括基板中心探索及定向、除氣、退火、沉積及/或蝕刻。根據一或更多實施例,群集工具包括至少一個第一腔室及一中心移送室。該中心移送室可容納機器人,該機器人可使基板往返於處理腔室與負載鎖定腔室之間及各處理腔室之間及各負載鎖定腔室之間。移送室通常維持在真空條件下,且移送室提供中間平臺,該中間平臺用於使基板自一腔室至另一腔室及/或至負載鎖定腔室往返,該負載鎖定腔室定位於群集工具之前端。經調適可
用於本發明之兩種眾所熟知的群集工具為Centura®及Endura®,Centura®及Endura®兩者均可購自於加利福尼亞州聖克拉拉市的應用材料公司。發表於1993年2月16日,Tepman等人所著的標題為「Staged-Vacuum Wafer Processing Apparatus and Method」之美國專利第5,186,718號中揭示了一種此類分級真空基板處理設備的詳細內容。儘管如此,為達成執行如本文所描述之製程的特定步驟之目的,腔室之具體配置及組合可經改變。可使用之其他處理腔室可包括但不限於:循環層沉積(CLD)、原子層沉積(ALD)、化學氣相沈積(CVD)、物理氣相沈積(PVD)、蝕刻、預清洗、化學清洗、熱處理(諸如RTP)、電漿氮化、除氣、定向、羥基化及其他基板製程。藉由在群集工具上之腔室中執行製程,可避免基板之表面污染與大氣雜質,使基板不在沉積隨後的薄膜之前發生氧化。
根據一或更多實施例,該基板連續地處於真空或「負載鎖定」條件下,且在從一腔室移動至下一個腔室時,該基板並未曝露於周圍空氣。因此,該等移送室在真空條件下,且該等移送室被「排空」至真空壓力下。惰性氣體可存在於處理腔室或移送室中。在一些實施例中,將惰性氣體用作淨化氣體,以在基板之表面上形成層之後移除一些或全部的反應物。根據一或更多實施例,將淨化氣體注入沉積腔室之出口,以防止反應物自沉積腔室移動至移送室及/或額外的處理腔室。因此,該惰性氣體流在腔室之出口處形成屏障。
可在單一基板沉積腔室中處理基板,在該沉積腔室
中,在處理另一基板之前,一單一基板經加載、處理且卸載。亦可以連續方式(如傳送帶系統)處理該基板,在該種方式中,將多個基板單獨地載入腔室之第一部分,移動穿過該腔室,且自該腔室之第二部分卸載。該腔室及相關傳送帶系統之形狀可形成直線路徑或曲線路徑。另外,處理腔室可為旋轉式傳送,其中多個基板圍繞中心軸移動,且經曝露以在旋轉式傳送路徑各處進行沉積、蝕刻、退火、清洗等製程。
在處理期間,該基板可經加熱或冷卻。該加熱或冷卻可藉由任何適當的方式完成,該等方式包括但不限於改變基板支撐件的溫度,及使加熱或冷卻氣體流動至基板表面。在一些實施例中,基板支撐件包括加熱器/冷卻器,該加熱器/冷卻器可經控制以傳導性地改變基板溫度。在一或更多實施例中,所採用之氣體(反應氣體或惰性氣體)可經加熱或冷卻,以局部地改變基板溫度。在一些實施例中,將加熱器/冷卻器定位於腔室內,鄰近於基板表面,以對流地改變基板溫度。
在處理期間,基板亦可為固定的或旋轉的。旋轉基板可經連續地旋轉或以不連續的步驟旋轉。舉例而言,在整個製程中可一直旋轉基板,或在曝露基板至不同反應氣體或淨化氣體之步驟間少量地旋轉基板。在處理期間(連續或分步地)旋轉基板可藉由最小化例如氣體流動幾何中局部變化之效應,而助於產生更均勻之沉積或蝕刻。
在原子層沉積類型腔室中,可將基板曝露於製程空間上分離的或時間上分離的第一及第二前驅物。時間ALD為
傳統製程,在該製程中,第一前驅物流動至腔室中以與表面反應。在使該第二前驅物流動至腔室之前,將第一前驅物從腔室中清除。在空間ALD中,第一前驅物及第二前驅物兩者同時流動至腔室,但兩種前驅物在空間上經分離,以便在該等氣體流之間具有一區域,該區域防止該等前驅物混合。在空間ALD中,基板必須相對於氣體分配面板移動,或反之亦然。
本說明書通篇引用的「一(one/an)實施例」、「某些實施例」或「一或更多實施例」意謂關於實施例描述的特定特徵、結構、材料或特性包括於本發明之至少一個實施例中。因此,本說明書通篇多處出現的用語,諸如「在一或更多實施例中」、「在某些實施例中」或「在一(one/an)實施例中」不必代表本發明之同一實施例。此外,在一或更多實施例中,特定的特徵、結構、材料或特性可以任何適當的方式組合。
儘管本文參考特定實施例描述本發明,但應瞭解,此等實施例僅為本發明之原則及應用之說明。對熟習此項技術者將顯而易見的是,在不脫離本發明之精神及範疇的情況下,可對本發明之方法及設備做出多種修改及變化。因此,本發明意欲包括在隨附申請專利範圍及彼等效物之範疇內所作出的修改及變化。
實例
第1實例
將全部樣品加熱至90℃之溫度,並將該溫度保持18天之時間,且在18天中在不同的時間間隔量測非揮發性殘留物之百分比。錳前驅物之一者含有兩個雙(三甲基矽烷基)醯胺(TMSA)配位子。另一錳前驅物含有兩個TMSA配位子及兩個吡啶(py)配位子,且稱為「穩定化」前驅物。具有不銹鋼之實例表示習用安瓿,該安瓿通常添加有不銹鋼襯裡。具有SiO2之實例模擬具有襯裡之安瓿。非揮發性殘留物之百分比表示由於與該表面反應而損失的前驅物數量。亦即,非揮發性殘留物之百分比越高,前驅物損失越多。因此需要較低的百分比。
第2圖為一圖表,該圖表圖示18天內非揮發性殘留物的百分比,包括基於資料點之趨勢線。第1A實例(該實例含有位於被加熱之不銹鋼容器中的Mn(TMSA)2)提供基線製程,這是因為容器不含有襯裡,且該前驅物不含有額外的穩定化配位子。因此,第1A實例亦用作一基線,以用於與其他實例之對照。由該圖式可見,至第18天,約有17%之非揮發性殘留物。相比之下,具有同一前驅物之添加襯裡容器(第1B實例)僅顯示約7%之非揮發性殘留物,相當於下降了一半以上。第1C實例(該實例以不銹鋼容器中之穩定化前驅物為特徵)以與第1B實例之經添加襯裡的容器中不穩定的前驅
物比較之方式執行。亦即,在18天后,第1C實例顯示約7.5%之非揮發性殘留物,該殘留物亦少於第1A實例中所顯示的一半。第1D實例(該圖以穩定化前驅物及經添加襯裡之容器兩者為特徵)顯示最好的結果。18天后,第1D實例之資料的推斷顯示非揮發性殘留物之百分比(%)預期將為約3.5%,該百分比低於第1B實例及第1C實例,且顯著低於第1A實例。從此等實施例中看出穩定化該前驅物及/或為安瓿添加襯裡之優勢係明顯的。
第2實例
DursanTM及silcolloyTM代表使用兩種不同的矽基抗腐蝕塗層塗覆之不銹鋼標籤。此等標籤與樣品包括於一玻璃容器中(與第2A實例相同),且此等標籤將藉由將Mn(TMSA)2置放成與塗覆之不銹鋼接觸來模擬經添加襯裡之SST安瓿。該加熱容器模擬加熱安瓿經歷之條件。在不同時間間隔為每一樣品量測非揮發性殘留物之百分比。第3圖為一圖表,該圖表圖示在20天內非揮發性殘留物的百分比,包括該等資料點之趨勢線。如該圖式表明,多種具有金屬氧化物襯裡之容
器大大減少了非揮發性殘留物之百分比。
第3實例(對照實例)
第4圖為Mn(TMSA)2的熱解重量分析曲線,以及該曲線之導數。將該前驅物之重量作為溫度函數進行量測。少量的前驅物以2℃/分鐘穩定升溫。實線曲線表示重量,且虛線曲線表示重量的時間導數,以提供給定溫度下質量損失(亦即汽化)之速率。
第4實例
第4實例重複第3實例之試驗,除前驅物為Mn(TMSA)2(py)2之外(Mn(TMSA)2(py)2被視為穩定化前驅物)。再次,實線曲線表示重量,且虛線曲線表示重量之導數,以提供給定溫度下質量損失(亦即汽化)的速率。第5圖圖示熱解重量分析曲線及該熱解重量分析曲線之導數。由該圖式可見,與Mn(TMSA)2相比,具有吡啶配位子之穩定化前驅物具有增加之穩定性。
第5實例
第5實例重複第3實例之試驗,除前驅物為Mn(TMSA)2(TMEDA)之外(該Mn(TMSA)2(TMEDA)被視為穩定化前驅物)。再次,實線曲線表示重量,且虛線曲線表示重量之導數,以提供給定溫度下質量損失(亦即汽化)的速率。第6圖圖示熱解重量分析曲線及該熱解重量分析曲線之導數。由該圖式可見,與Mn(TMSA)2相比,穩定化前驅物具有增加之穩定性。另外,與Mn(TMSA)2相比,TMEDA穩定化前驅物不具有任何顯著的揮發性損失。雖然導數曲線所圖
示之頂點可意謂在彼等溫度下發生了一些分解,但是質量曲線到達零之事實意謂分解之產物仍為揮發性的,且可能為可接受的。
300‧‧‧來源罐
302‧‧‧載氣源
306‧‧‧處理腔室
312‧‧‧閥
314‧‧‧閥
402‧‧‧圓筒形側壁
404‧‧‧蓋
406‧‧‧進氣埠
408‧‧‧出氣埠
410‧‧‧擋板
414‧‧‧前驅物材料
416‧‧‧液體
418‧‧‧上部區域
420‧‧‧外殼
422‧‧‧進氣管
424‧‧‧第一端
426‧‧‧第二端
430‧‧‧電阻加熱器
432‧‧‧底部
436A‧‧‧斷開配件
436B‧‧‧斷開配件
438‧‧‧內部體積
444‧‧‧襯裡
450‧‧‧集油器
452‧‧‧集油器主體
454‧‧‧擋板
456‧‧‧中心線
Claims (17)
- 一種用於生成一化學前驅物氣體之設備,該設備包含:一罐,該罐具有一側壁、一頂端及一底部,該側壁、該頂端及該底部形成一內部體積;一進氣埠及一出氣埠,該進氣埠及該出氣埠與該內部體積流體連通;一襯裡,該襯裡在該側壁、頂端或底部之至少部分上,其中該襯裡包含一惰性金屬氧化物;以及一前驅物,該前驅物在該罐之該內部體積中,其中該前驅物含有至少一個Mn-N鍵及一2-電子供體配位子,其中該2-電子供體配位子包含吡啶、四氫呋喃或四氫噻吩、四甲基乙二胺、乙腈、三級胺或2,2’-聯吡啶。
- 如請求項1所述之設備,其中該襯裡位於該底部之至少部分上。
- 如請求項1所述之設備,其中該惰性金屬氧化物包含一介電質。
- 如請求項1所述之設備,其中該惰性金屬氧化物包含SiO2、Al2O3、TiO2、碳化矽、碳氧化矽或Ta2O5。
- 如請求項1所述之設備,其中該前驅物具有一結構,該結構表示為:
- 一種沉積一含錳薄膜之方法,該方法包含以下步驟:提供含有至少一個Mn-N鍵以及一2-電子供體配位子之一前驅物,其中該2-電子供體配位子包含吡啶、四氫呋喃或四氫噻吩、四甲基乙二胺、乙腈、三級胺或2,2’-聯吡啶;以及使該前驅物流動穿過用於生成一化學前驅物氣體之一設備,其中該設備具有包含一惰性金屬氧化物之一襯裡。
- 如請求項6所述之方法,其中該惰性金屬氧化物包含一介電質。
- 如請求項6所述之方法,其中該惰性金屬氧化物包含SiO2、Al2O3、TiO2、碳化矽、碳氧化矽或Ta2O5。
- 如請求項6所述之方法,其中該前驅物具有一結構,該結構表示為:
其中各A獨立地選自於碳或矽,且各R獨立地選自於氫、甲基、取代或非取代烷烴、支鏈或非支鏈烷烴、取代或非取代烯烴、支鏈或非支鏈烯烴、取代或非取代炔烴、支鏈或非支鏈炔烴或取代或非取代芳族物。 - 如請求項9所述之方法,其中各A為矽。
- 如請求項9所述之方法,其中各R基為甲基。
- 如請求項9所述之方法,其中該前驅物包含雙(雙三甲基矽烷基)醯胺錳。
- 如請求項11所述之方法,該方法進一步包含以下步驟:將一基板表面曝露於該雙(雙三甲基矽烷基)醯胺錳及包含NH3之一第二前驅物。
- 如請求項6所述之方法,其中至少Mn-N鍵為該2-電子供體配位子之部分。
- 如請求項14所述之方法,其中該前驅物具有一結構,該 結構表示為:
- 如請求項6所述之方法,其中該方法進一步包含以下步驟:將一基板表面曝露於該前驅物。
- 一種沉積一含錳薄膜之方法,該方法包含以下步驟:將一基板表面曝露於該汽化前驅物,其中該前驅物包含:
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| US9196474B2 (en) | 2015-11-24 |
| CN112323039A (zh) | 2021-02-05 |
| US20140242806A1 (en) | 2014-08-28 |
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| CN105026613A (zh) | 2015-11-04 |
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| KR102271767B1 (ko) | 2021-06-30 |
| JP6411385B2 (ja) | 2018-10-24 |
| WO2014134481A1 (en) | 2014-09-04 |
| JP2016513185A (ja) | 2016-05-12 |
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