CN109478496A - 硅硫族化物前体、形成硅硫族化物前体的方法和形成氮化硅以及半导体结构的相关方法 - Google Patents
硅硫族化物前体、形成硅硫族化物前体的方法和形成氮化硅以及半导体结构的相关方法 Download PDFInfo
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- CN109478496A CN109478496A CN201780044631.5A CN201780044631A CN109478496A CN 109478496 A CN109478496 A CN 109478496A CN 201780044631 A CN201780044631 A CN 201780044631A CN 109478496 A CN109478496 A CN 109478496A
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- Prior art keywords
- silicon
- precursor
- substituted
- chalkogenide
- silicon nitride
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 156
- 239000002243 precursor Substances 0.000 title claims abstract description 151
- 239000010703 silicon Substances 0.000 title claims abstract description 143
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 238000000034 method Methods 0.000 title claims abstract description 80
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 75
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000004065 semiconductor Chemical group 0.000 title claims abstract description 32
- 125000003368 amide group Chemical group 0.000 claims abstract description 67
- 150000004703 alkoxides Chemical group 0.000 claims abstract description 37
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 34
- 125000005843 halogen group Chemical group 0.000 claims abstract description 33
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011669 selenium Chemical group 0.000 claims abstract description 16
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229910052714 tellurium Chemical group 0.000 claims abstract description 11
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005864 Sulphur Substances 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 70
- 239000000758 substrate Substances 0.000 claims description 47
- -1 tetramethyl selenic acid silicon Chemical compound 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 23
- 238000000231 atomic layer deposition Methods 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 21
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 19
- 150000001787 chalcogens Chemical class 0.000 claims description 14
- 238000005229 chemical vapour deposition Methods 0.000 claims description 14
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 229910052798 chalcogen Inorganic materials 0.000 claims description 8
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 125000001979 organolithium group Chemical group 0.000 claims description 6
- 239000005049 silicon tetrachloride Substances 0.000 claims description 6
- 230000008542 thermal sensitivity Effects 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 claims description 4
- NNOVOXCGEFMJRK-UHFFFAOYSA-N [Li]C.[SeH2] Chemical compound [Li]C.[SeH2] NNOVOXCGEFMJRK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- XKLVLDXNZDIDKQ-UHFFFAOYSA-N butylhydrazine Chemical group CCCCNN XKLVLDXNZDIDKQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 description 44
- 230000009257 reactivity Effects 0.000 description 13
- 239000002585 base Substances 0.000 description 8
- 238000005240 physical vapour deposition Methods 0.000 description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 239000012686 silicon precursor Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- AFYNYVFJTDCVBJ-UHFFFAOYSA-N [Si].[S] Chemical compound [Si].[S] AFYNYVFJTDCVBJ-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910020776 SixNy Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- 101100373011 Drosophila melanogaster wapl gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 238000001321 HNCO Methods 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 206010037211 Psychomotor hyperactivity Diseases 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 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
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 210000004483 pasc Anatomy 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 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
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- HUKGIVMVTNTTRT-UHFFFAOYSA-J silicon(4+) tetraiodate Chemical compound I(=O)(=O)[O-].[Si+4].I(=O)(=O)[O-].I(=O)(=O)[O-].I(=O)(=O)[O-] HUKGIVMVTNTTRT-UHFFFAOYSA-J 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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
- H01L21/02205—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 the layer being characterised by the precursor material for deposition
- H01L21/02208—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
-
- 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
- C07F7/02—Silicon compounds
- C07F7/025—Silicon compounds without C-silicon linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/04—Coating on selected surface areas, e.g. using masks
- C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
-
- C—CHEMISTRY; METALLURGY
- 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
- C23C16/345—Silicon nitride
-
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Abstract
本申请案涉及硅硫族化物前体、形成所述硅硫族化物前体的方法和形成氮化硅以及半导体结构的相关方法。本发明揭示一种硅硫族化物前体,其包含化学式Si(XR1)nR2 4‑n,其中X为硫、硒或碲,R1为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,各R2独立地为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,且n为1、2、3或4。本发明还揭示形成所述硅硫族化物前体的方法、形成氮化硅的方法和形成半导体结构的方法。
Description
优先权主张
本申请案主张于2016年7月20日提出申请的美国专利申请案第15/215,102号“硅硫族化物前体、形成硅硫族化物前体的方法和形成氮化硅以及半导体结构的相关方法(Silicon Chalcogenate Precursors,Methods of Forming the Silicon ChalcogenatePrecursors,and Related Methods of Forming Silicon Nitride and SemiconductorStructures)”的申请日期的益处。
技术领域
本文所揭示的实施例涉及半导体制作,其包括用于形成氮化硅的前体化合物、形成前体化合物的方法、形成氮化硅的方法和形成半导体结构的方法。更具体来说,本发明的实施例涉及硅硫族化物前体、形成硅硫族化物前体的方法、使用硅硫族化物前体形成氮化硅的方法和形成半导体结构的方法。
背景技术
氮化硅(SiN)为制造集成电路(IC)广泛使用的材料。由于其低反应性和高热稳定性,氮化硅用作绝缘材料、遮罩材料、蚀刻终止材料、障壁材料、间隔材料等。
形成SiN的技术包括物理气相沉积(PVD)和化学气相沉积(CVD),例如高温热CVD或等离子体增强的CVD(PECVD)。在一个工艺中,使硅烷(SiH4)与氨(NH3)反应以形成SiN。可使用其它硅前体,例如卤化硅,包括氟化硅、氯化硅、碘化硅或溴化硅。卤化硅的实例包括(但不限于)四氯化硅(SiCl4)或二氯硅烷(SiCl2H2)、三氯硅烷(SiHCl3)、HSiI3、H2SiI2、H3SiI、H2Si2I4、H4Si2I2或H5Si2I。为形成高质量SiN,在高温(通常高于750℃)下进行PVD和CVD工艺。然而,这些温度与当前IC中所使用的材料不相容,其中一些具热敏性。另外,使用卤化硅作为硅前体为不合意的,这是因为产生诸如盐酸(HCl)的反应性卤化物物质作为副产物。已知反应性卤化物物质蚀刻半导体制作中所用的材料,例如含硅材料。
原子层沉积(ALD)还已用于形成SiN。硅烷、卤化硅和氨CVD前体在高温下或在等离子体环境中具有足够反应性以通过ALD形成SiN。然而,前体在低温下或无等离子体的情形下无足够反应性。尽管已使用等离子体增强的ALD(PEALD)来形成SiN,且与CVD工艺的保形性和沉积温度相比,已实现增加的保形性和增加的沉积温度,但SiN的阶梯覆盖的保形性不足以覆盖当前IC中所存在的复杂形貌。另外,在PEALD工艺的等离子体部分期间所产生的激发物质对IC上的暴露材料无选择性,且因此出现激发物质与暴露材料之间的非预期反应。即使在不存在等离子体的情况下,也需要谨慎地选择硅前体以避免这些非预期反应,所述非预期反应可导致IC性能的退化。
还已提出基于硅烷胺的化合物,例如双[(二甲基氨基)甲基硅基](三-甲基硅基)胺、双[(二乙基氨基)二甲基硅基](三甲基硅基)胺或三[(二乙基氨基)-二甲基硅基]胺作为硅前体用于ALD工艺。
随着SiN的沉积需求变得更加严格,上文所提及的技术已不能以所需保形度和在低温下形成SiN。
附图说明
图1为包括氮化硅材料的半导体结构的简化剖面图,所述氮化硅材料是根据本发明的实施例所形成;且
图2为硅-配体(Si-R)系统与氨的反应的活化能(Ea)随能量变化(dE)而变化的图形。
具体实施方式
本发明揭示硅硫族化物前体,同样揭示形成硅硫族化物前体的方法和使用硅硫族化物前体形成氮化硅(SiN)的方法。可在低温和不使用等离子体的情形下通过ALD工艺在衬底上形成SiN。硅硫族化物前体可与还原剂充分反应,以在ALD工艺的反应条件下形成SiN同时仍展现稳定性。通过本发明的方法形成的SiN可具有高保形度,例如大于约90%的阶梯覆盖率,使得SiN能够在高密度、高纵横比的半导体结构上形成。由于SiN为在低温下形成,因此本发明的方法与可在ALD工艺期间暴露的热敏性材料相容。另外,尽管硅硫族化物前体可包括卤素原子,但本发明的方法不产生反应性含卤素物质(即,不含反应性含卤素物质)且不使用等离子体(即,无等离子体)。因此硅硫族化物前体为卤化硅前体的适宜替代物。
如本文中所使用,术语“硅硫族化物”意指并包括含有至少一个硅原子和至少一个硫族元素原子的化合物,且包括至少一个硅-硫族元素键。硅硫族化物类似于硅醇盐,只是用硫原子、硒原子或碲原子替代硅醇盐的氧原子。硫族元素包括周期表第VI族的元素,例如硫、硒或碲。
如本文中所使用,术语“氮化硅”意指并包括含有硅原子和氮原子的化合物。氮化硅可包括化学计量量的硅和氮(例如,Si3N4)或可包括非化学计量量的硅和氮(例如,SixNy),其中x和y中的每一者独立地为约0.5到约2.0的有理数。氮化硅还可包括Si(CH)xNy,其中x和y中的每一者独立地为约0到约2.0的有理数。
如本文中所使用,术语“衬底”意指并包括在其上形成其它材料的基底材料或构筑体。衬底可为半导体衬底、支撑结构上的基底半导体层、金属电极或其上形成有一或多个材料、层、结构或区域的半导体衬底。半导体结构上的材料可包括(但不限于)半导电材料、绝缘材料、导电材料等。所述材料中的一或多者可具热敏性。衬底可为常规硅衬底或包含半导电材料层的其它块状衬底。如本文中所使用,术语“块状衬底”不仅意指并包括硅晶片,而且意指并包括绝缘体上硅(“SOI”)衬底(例如,蓝宝石上硅(“SOS”)衬底和玻璃上硅(“SOG”)衬底)、基底半导体底座上的硅的外延层和其它半导体或光电子材料(例如,硅锗、锗、砷化镓、氮化镓和磷化铟)。衬底可经掺杂或未经掺杂。
如本文中所使用,术语“纵横比”意指并包括特征的高度对特征的宽度的比率。
以下说明提供具体细节(例如,材料类型、材料厚度和处理条件),以便提供对本文所述实施例的透彻说明。然而,所属领域技术人员将理解,可在不采用这些具体细节的情形下实践本文所揭示的实施例。实际上,实施例可结合半导体工业中所采用的常规制作技术来实践。另外,本文所提供的说明不形成半导体结构的完整说明或制造半导体结构的完整工艺流程,且下文所阐述的结构不形成完整的半导体结构。下文仅详细地阐述理解本文所述实施例所必需的那些工艺措施和结构。形成包括本文所述结构的完整半导体结构的其它措施可通过常规技术来实施。
硅硫族化物前体可具有化学式Si(XR1)nR2 4-n,其中X为硫、硒或碲,R1为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,各R2独立地为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基或卤化物基团,且n为1、2、3或4。独立地选择X、R1和R2中的每一者,以提供硅硫族化物前体与还原剂所需反应性并提供硅硫族化物前体所需稳定性。各R2可独立地包括直接或间接键结到硅原子的卤素原子,而剩余取代基(即,R1)仅包括间接键结到硅原子的卤素原子(如果其存在)。因此,硅硫族化物前体中可存在多个卤素原子。
如本文中所使用,术语“烷基”意指并包括含有1个碳原子(C1)到10个碳原子(C10)(例如1个碳原子(C1)到6个碳原子(C6))的饱和、不饱和、直链、具支链或环状烃链。
如本文中所使用,术语“醇盐”意指并包括连接到氧原子的烷基,包括(但不限于)甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基或癸氧基,或经烷氧基取代的烷氧基(例如,聚醚基团),例如甲氧基甲氧基、甲氧基乙氧基、乙氧基甲氧基、乙氧基乙氧基、甲氧基乙氧基乙氧基等。
如本文中所使用,术语“经取代”意指并包括官能基的其中一或多个氢原子由另一官能基替代,例如烷基、醇盐基、酰胺基、胺基或卤素基团。
如本文中所使用,术语“酰胺”意指并包括-NR'R”基团,其中R'和R”独立地为烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团。
如本文中所使用,术语“胺”意指并包括-NH2基团。
如本文中所使用,术语“卤素”意指并包括氟、氯、溴或碘。
硅硫族化物前体可具有以下化学式:
其中X、R1和R2是如上文所定义且R3和R4中的每一者独立地为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基或卤化物基团。硅硫族化物前体可替代地包括2、3或4个直接键结到硅原子的-X-基团,例如Si(XR1)(XR2)(R3)(R4)、Si(XR1)(R2)(XR3)(R4)、Si(XR1)(XR2)(R3)(XR4)、Si(XR1)(XR2)(XR3)(R4)、Si(XR1)(R2)(XR3)(XR4)或Si(XR1)(XR2)(XR3)(XR4)。在一个实施例中,硅硫族化物为四甲基硒酸硅(Si(Se(CH3)4))。
X、R1和R2基团和n的值可基于SiN的预期应用来选择。例如,如果需要高度反应性和稳定性的硅硫族化物前体,则硅硫族化物前体可包括4个硫族元素原子,例如具有化学式Si(XR1)(XR2)(XR3)(XR4)的化合物。然而,如果需要较低反应性和稳定性的硅硫族化物前体,则硅硫族化物前体可包括较少硫族元素原子,即具有以下化学式的化合物:Si(XR1)(R2)(R3)(R4)、Si(XR1)(XR2)(R3)(R4)、Si(XR1)(R2)(XR3)(R4)、Si(XR1)(XR2)(R3)(XR4)、Si(XR1)(XR2)(XR3)(R4)或Si(XR1)(R2)(XR3)(XR4)。
如果存在卤素原子以在与还原剂的反应性与稳定性之间提供所需平衡,则R2、R3和R4中的每一者都可包括直接或间接键结到硅原子的卤素原子。举例来说,预计R2、R3和R4中的每一者都可包括直接或间接键结到硅原子的卤素原子。如果R1上存在卤素原子,则卤素原子通过硫族元素原子X间接键结到硅原子。在其中仅R1包括卤素原子的情形中,卤素原子为通过硫族元素原子X间接键结到硅硫族化物前体的硅原子。因此,在R1位无直接硅-卤素键,这是因为硫族元素原子直接键结到硅原子,且卤素原子直接键结到硫族元素原子。在其中R2、R3或R4中的一或多者包括卤素原子的情形中,卤素原子可直接或间接键结到硅原子。为提供硅硫族化物前体的反应性与稳定性的所需平衡,R2、R3或R4中的一或多者独立地包括直接或间接键结到硅原子的卤素原子,而剩余取代基(即,R1)仅包括间接键结到硅原子的卤素原子(如果其存在)。
因此,本发明揭示硅硫族化物前体且其包含化学式Si(XR1)nR2 4-n,其中X为硫、硒或碲,R1为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,各R2独立地为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,且n为1、2、3或4。
根据本发明实施例的硅硫族化物前体与还原剂(例如,含氮前体)充分反应,以通过ALD工艺形成SiN。然而,硅硫族化物前体还足够稳定以在ALD工艺的蒸气递送条件下使用。硅硫族化物前体展现与常规卤化硅前体相似的与还原剂的反应性。含氮前体可包括(但不限于)氨(NH3)、肼(N2H4)、叔丁基肼、单烷基肼、二烷基肼或其组合。在一个实施例中,含氮前体为氨。硅硫族元素前体用作SiN的硅源且含氮前体用作SiN的氮源。
尽管根据本发明实施例的硅硫族化物前体可包括多个卤素原子,然而硅硫族化物前体可与存在于衬底上且在ALD工艺期间暴露的敏感材料相容,这是因为不产生反应性含卤素物质作为副产物。因此,在ALD工艺期间未观察到卤化物副产物污染。
可通过使有机锂试剂或格氏试剂(Grignard reagent)与硫族元素源化合物反应,以产生有机锂硫族元素化合物来形成硅硫族化物前体。有机锂试剂可根据硅硫族化物前体的所需R1和R2基团来适当地选择。有机锂可包括烷基锂试剂,例如甲基锂、乙基锂等。硫族元素源化合物可根据硅硫族化物前体的所需硫族元素来适当地选择。硫族元素源化合物可为元素硫、元素硒、元素碲或其组合。然后可使有机锂硫族元素化合物与卤化硅化合物反应,以形成硅硫族化物前体。卤化硅可包括(但不限于)硅和氟的化合物、硅和氯的化合物、硅和溴的化合物或硅和碘的化合物。有机锂硫族元素化合物和卤化硅可在(例如)低于室温或低于0℃的低温下反应以产生硅硫族化物前体。
因此,本发明揭示形成硅硫族化物前体的方法。所述方法包含使有机锂试剂与硫族元素源化合物反应,以产生有机锂硫族元素化合物。使有机锂硫族元素化合物与卤化硅化合物反应,以形成硅硫族化物前体。硅硫族化物前体包含化学式Si(XR1)nR2 4-n,其中X为硫、硒或碲,R1为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,各R2独立地为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,且n为1、2、3或4。
为通过ALD形成SiN,可将硅硫族化物前体和含氮前体相继引入含有衬底的反应器中并使前体与衬底表面反应。可将硅硫族化物前体引入反应器中,使其与衬底反应并将过量未反应的硅硫族化物前体从反应器吹扫出,以在衬底上形成硅。可形成单层或较少的硅。然后可将含氮前体引入反应器中,使其与衬底上的硅反应,并将过量未反应的含氮前体从反应器吹扫出,以在硅上形成氮。可形成单层或更少的氮。反应器可为常规反应室或常规沉积室,例如常规ALD反应器或常规CVD反应器,在此不对其进行详细阐述。在ALD工艺期间,使来自硅硫族化物前体的硅和来自含氮前体的氮吸附到衬底表面。可逆转引入硅硫族化物前体和含氮前体的顺序,使得将含氮前体引入反应器中,与衬底表面反应并将过量未反应的含氮前体从反应器吹扫出,以在衬底上形成氮。然后,可将硅硫族化物前体引入反应器中,与氮反应,并将过量未反应的硅硫族化物前体从反应器吹扫出,以在氮上形成硅。硅硫族化物前体和含氮前体的引入可任选地包括载气,例如氦、氩、氮或其组合。可将相继引入硅硫族化物前体和含氮前体的工艺重复所需循环数,直到获得所需厚度的SiN为止。在每次引入硅硫族化物前体和含氮前体中间,反应器可任选地经吹扫气体吹扫,以去除未反应的硅硫族化物前体和含氮前体或反应副产物。吹扫气体可为惰性气体,例如氦、氩、氮或其组合。
在其中含氮前体为氨的实施例中,ALD工艺可根据以下反应来进行:
Si(XR1 n)R2 4-n+NH3→SixNy+HXR1+HR2。
ALD工艺可在小于或等于约350℃、例如小于或等于约250℃的温度下进行。在发生ALD工艺时,反应器内和衬底的温度可为约350℃或低于约350℃。相对于形成SiN的常规高温热CVD、PECVD或PVD工艺的温度,形成SiN的低温可降低热预算。低温还可使得能够保形地形成SiN,但敏感材料存在于衬底上。不受限制,敏感材料可包括(但不限于)硫族化物材料、有机(例如,碳)材料、碳同素异形体(例如,石墨)、反应性金属(例如,钨、铝或钽)或其它敏感材料。因此,SiN可毗邻此等敏感材料形成,而不降解、分解或以其它方式负面地影响所述材料。
可将硅硫族化物前体、含氮前体和吹扫气体中的每一者以约1标准立方厘米(sccm)到约2000sccm(例如约1sccm到约1000sccm)的流速引入反应器中。硅硫族化物前体和含氮前体中的每一者都可在反应器中存留约0.1秒到100秒范围内的时间量,足以使硅硫族化物前体与含氮前体反应。
硅硫族化物前体和含氮前体可具有足够反应性,使得不需要等离子体。因此,ALD工艺可在不生成等离子体的情形下进行。然而,根据衬底上毗邻和暴露材料的热敏性,可使用等离子体来增加硅硫族化物前体与含氮前体的反应性。例如,如果衬底上的毗邻和暴露材料不具热敏性或具较小热敏性,则可增加沉积温度或可使用等离子体。可在反应器中生成等离子体(例如,直接等离子体)或可在反应器外生成等离子体并供应到反应器(例如,远程等离子体)。
不受任何理论束缚,据信,根据本发明实施例的硅硫族化物前体稳定,但展现与常规卤化硅前体相似的与含氮前体的反应性。因此,根据本发明实施例的硅硫族化物前体热稳定且不易于分解。仅举例来说,如果硅硫族化物前体为四甲基硒酸硅(Si(SeCH3)4),则硅硫族化物前体可根据以下途径之一分解:
分解途径 | E<sub>a</sub>(kJ/mol) | dE(kJ/mol) |
Si(SeCH<sub>3</sub>)<sub>4</sub>→SiH(SeCH<sub>3</sub>)<sub>3</sub>+SeCH<sub>2</sub> | 347.1 | 183.9 |
Si(SeCH<sub>3</sub>)<sub>4</sub>→SiSe(SeCH<sub>3</sub>)<sub>2</sub>+Se(CH<sub>3</sub>)<sub>2</sub> | 246.1 | 56.7 |
Si(SeCH<sub>3</sub>)<sub>4</sub>→Si(SeCH<sub>3</sub>)<sub>2</sub>+CH<sub>3</sub>SeSeCH<sub>3</sub> | 300.9 | 214.5 |
Si(SeCH<sub>3</sub>)<sub>4</sub>→Si(CH<sub>3</sub>)<sub>2</sub>(SeCH<sub>3</sub>)<sub>2</sub>+Se<sub>2</sub> | 293.0 | 118.5 |
据信,分解路径的高活化能(Ea)(即,能量障壁)和吸热性质为硅硫族化物前体提供所需性质。
因此,本发明揭示形成SiN的方法。所述方法包含使硅硫族化物前体与含氮前体反应以形成氮化硅。硅硫族化物前体包含化学式Si(XR1)nR2 4-n,其中X为硫、硒或碲,R1为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,各R2独立地为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,且n为1、2、3或4。
因此,本发明揭示另一形成SiN的方法。所述方法包含使硅硫族化物前体与衬底反应以在衬底上形成硅,使硅与含氮前体反应以在硅上形成氮,和重复使硅硫族化物前体反应和使硅与含氮前体反应的行为。硅硫族化物前体包含化学式Si(XR1)nR2 4-n,其中X为硫、硒或碲,R1为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,各R2独立地为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,且n为1、2、3或4。
仅举例来说,可形成厚度在几个单层到约100nm(例如约1nm到约100nm或约5nm到约50nm)范围内的SiN。然而,还可形成更大厚度的SiN。
本文所包括的图解说明并非打算为任何具体半导体结构的实际视图,而仅为为阐述本文实施例所采用的理想化代表图。因此,图解说明可不按比例绘制。
如图1中所显示,SiN 100可在半导体结构102上保形地形成,所述半导体结构具有至少一个具有高纵横比的特征104。半导体结构102可包括衬底106,其具有界定特征104的开口108。根据SiN 100的期望应用,衬底106可为半导电材料、绝缘材料或导电材料。仅举例来说,半导电材料可为硅、氧化硅、镓等。仅举例来说,绝缘材料可为二氧化硅、二氧化铪、氧化铝。仅举例来说,导电材料可为金属、导电掺杂的硅、导电掺杂的锗、金属硅化物、金属碳化物、相变材料等。衬底106的材料可通过常规技术形成,例如物理气相沉积(PVD)、化学气相沉积(CVD)或原子层沉积(ALD)。此等技术为业内已知,且因此在本文中不进行详细阐述。如图1中所显示,特征104为从衬底106的材料形成。然而,衬底106可在其上包括组成特征104的一或多个材料、层、结构或区域,例如堆叠结构。堆叠结构的材料可通过常规技术形成,在本文中不对其进行详细阐述。特征104可具有高纵横比,例如至少10:1(例如至少12:1或至少15:1)的纵横比。根据本发明的实施例,SiN 100可于特征104上方形成。或者,SiN100可在半导体结构102上作为平面层形成(未显示)。SiN可在任何半导体装置结构(例如,晶体管、存储器、逻辑装置、存储器阵列等)中用作绝缘材料、遮罩材料、蚀刻终止材料、障壁材料或间隔材料。半导体装置结构可包括至少一个高纵横比特征。
因此,本发明揭示形成半导体结构的方法。所述方法包含形成包含至少一个纵横比大于约10的特征的衬底,和使硅硫族化物前体与含氮前体反应以在至少一个特征上形成氮化硅。
尽管上文阐述通过ALD工艺形成SiN的方法,但硅硫族化物前体还可在CVD工艺中用作硅前体。所述CVD工艺实质上可如上文所阐述,只是硅硫族化物前体和含氮前体是同时引入CVD反应器中,且适当操作条件是针对CVD工艺所选择。
以下实例用于更详细地解释本发明的实施例。对于本发明的范围来说,不应将这些实例理解为详尽的或排他的。
实例
四甲基硒酸硅的合成
如在以下反应方案中所显示,使略微过量的甲基锂(MeLi)与硒(Se)在四氢呋喃或二甘二甲醚中反应,以形成甲基硒化锂(LiSeMe)。使四当量的LiSeMe与四氯化硅在-76℃下反应,以形成四甲基硒酸硅,将其回收。
活化能和能量变化计算
针对Si(SeCH3)4与NH3的反应进行密度泛函理论(DFT)计算。为比较,针对SiCl4与NH3的反应进行相似计算。所计算的活化能(Ea)和能量变化(dE)显示于下文中:
反应 | E<sub>a</sub>(kJ/mol) | dE(kJ/mol) |
Si(SeCH<sub>3</sub>)<sub>4</sub>+NH<sub>3</sub> | 132.1 | -16.9 |
SiCl<sub>4</sub>+NH<sub>3</sub> | 116 | -9.2 |
经测定,两个反应都放热并展现相似的能量障壁(分别为132.1kJ/mol和116kJ/mol)。
四甲基硒酸硅和四氯化硅对氨相当的反应性另人惊讶,这是因为其中氧原子替代硫族元素原子的类似前体不具相似反应性。
不同硅-配体系统对Ea/dE的效应
计算不同硅-配体(Si-R)系统与氨的反应的活化能(Ea)(即,能量障壁)和能量变化(dE),以测定配体(R)对键强度的效应。配体包括H、I、Cl、CN、NCO或SeCH3。图2显示对于每一Si-R系统活化能(Ea)随能量变化(dE)而变化的图形。根据所使用的Si-R系统,产生H2、HCl、HCN、HI、HNCO或MeSeH作为副产物。展现MeSeH消除的硅硫族化物前体较展现H2消除的Si-R系统具有更低活化能。尽管其它Si-R系统较包括硒者展现更低活化能,但这些Si-R系统的dE不如包括硒的Si-R系统有利。包括硒的Si-R系统较硅-氯系统具有略微更高的活化能。然而,由于硅-SeCH3系统不产生卤化物副产物,故未观察到与材料的不合意蚀刻相关的问题。
尽管已结合各图阐述某些说明性实施例,但所属领域技术人员将认识到并了解,本发明所涵盖的实施例并不限于本文中明确显示并阐述的所述实施例。而是,可在不背离本发明所涵盖实施例范围的情形下对本文所阐述的实施例进行许多添加、删除和修改,例如后文中所主张者,包括合法等效内容。另外,可将来自一个所揭示实施例的特征与另一所揭示实施例的特征组合,同时仍涵盖在本发明的范围内。
Claims (19)
1.一种形成氮化硅的方法,其包含:
使硅硫族化物前体与含氮前体反应以形成氮化硅,所述硅硫族化物前体包含化学式Si(XR1)nR2 4-n,其中X为硫、硒或碲,R1为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,各R2独立地为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,且n为1、2、3或4。
2.根据权利要求1所述的方法,其中使硅硫族化物前体与含氮前体反应以形成氮化硅包含通过原子层沉积形成所述氮化硅。
3.根据权利要求1所述的方法,其中使硅硫族化物前体与含氮前体反应以形成氮化硅包含通过化学气相沉积形成所述氮化硅。
4.根据权利要求1所述的方法,其中使硅硫族化物前体与含氮前体反应以形成氮化硅包含在衬底上保形地形成所述氮化硅。
5.根据权利要求1所述的方法,其中使硅硫族化物前体与含氮前体反应以形成氮化硅包含使所述硅硫族化物前体与氨、肼、叔丁基肼、单烷基肼、二烷基肼或其组合反应。
6.根据权利要求1所述的方法,其中使硅硫族化物前体与含氮前体反应以形成氮化硅包含在小于或等于约350℃的温度下形成所述氮化硅。
7.根据权利要求1所述的方法,其中使硅硫族化物前体与含氮前体反应以形成氮化硅包含在小于或等于约250℃的温度下形成所述氮化硅。
8.根据权利要求1所述的方法,其中使硅硫族化物前体与含氮前体反应以形成氮化硅包含使所述硅硫族化物前体与所述含氮前体在无等离子体环境中反应。
9.根据权利要求1所述的方法,其中使硅硫族化物前体与含氮前体反应以形成氮化硅包含:
使所述硅硫族化物前体与衬底反应以在所述衬底上形成硅;
使所述硅与所述含氮前体反应以在所述硅上形成氮;和
重复使所述硅硫族化物前体反应和使所述硅与所述含氮前体反应的行为以在所述衬底上形成所述氮化硅。
10.根据权利要求9所述的方法,其中使所述硅硫族化物前体与衬底反应以在所述衬底上形成硅包含使包含以下各项的硅硫族化物前体与所述衬底反应:Si(XR1)(R2)(R3)(R4)、Si(XR1)(XR2)(R3)(R4)、Si(XR1)(R2)(XR3)(R4)、Si(XR1)(XR2)(R3)(XR4)、Si(XR1)(XR2)(XR3)(R4)、Si(XR1)(R2)(XR3)(XR4)或Si(XR1)(XR2)(XR3)(XR4)。
11.根据权利要求9所述的方法,其中使所述硅硫族化物前体与衬底反应以在所述衬底上形成硅包含使四甲基硒酸硅与所述衬底反应。
12.一种形成半导体结构的方法,其包含:
形成包含至少一个具有大于约10的纵横比的特征的衬底;和
使硅硫族化物前体与含氮前体反应以在所述至少一个特征上形成氮化硅。
13.根据权利要求12所述的方法,其中使硅硫族化物前体与含氮前体反应以在所述至少一个特征上形成氮化硅包含在所述至少一个特征上保形地形成所述氮化硅。
14.根据权利要求12所述的方法,其中形成包含至少一个具有大于约10的纵横比的特征的衬底包含在热敏性衬底上形成所述至少一个特征。
15.根据权利要求12所述的方法,其中使硅硫族化物前体与含氮前体反应以在所述至少一个特征上形成氮化硅包含在可经卤化物蚀刻的所述至少一个特征上形成所述氮化硅。
16.一种硅硫族化物前体,其包含:
化学式Si(XR1)nR2 4-n,其中X为硫、硒或碲,R1为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,各R2独立地为氢、烷基、经取代的烷基、醇盐基、经取代的醇盐基、酰胺基、经取代的酰胺基、胺基、经取代的胺基或卤素基团,且n为1、2、3或4,
其中所述硅硫族化物前体不为四甲基硒酸硅。
17.一种形成根据权利要求16所述的硅硫族化物前体的方法,所述方法包含:
使有机锂试剂与硫族元素源化合物反应以产生有机锂硫族元素化合物;和
使所述有机锂硫族元素化合物与卤化硅化合物反应以形成所述硅硫族化物前体。
18.根据权利要求17所述的方法,其中使有机锂试剂与硫族元素源化合物反应包含使甲基锂与元素硒反应以形成甲基硒化锂。
19.根据权利要求17所述的方法,其中使所述有机锂硫族元素化合物与卤化硅化合物反应包含使甲基硒化锂与四氯化硅反应以形成四甲基硒酸硅。
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