CN100356519C - 二氧化铪层用前体及利用该前体生成二氧化铪膜的方法 - Google Patents
二氧化铪层用前体及利用该前体生成二氧化铪膜的方法 Download PDFInfo
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- CN100356519C CN100356519C CNB031530850A CN03153085A CN100356519C CN 100356519 C CN100356519 C CN 100356519C CN B031530850 A CNB031530850 A CN B031530850A CN 03153085 A CN03153085 A CN 03153085A CN 100356519 C CN100356519 C CN 100356519C
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- Prior art keywords
- hafnium oxide
- precursor
- oxide layer
- nitrogen compound
- hfcl
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- 229910000449 hafnium oxide Inorganic materials 0.000 title claims abstract description 117
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000002243 precursor Substances 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 56
- 229910017464 nitrogen compound Inorganic materials 0.000 title claims abstract description 28
- 150000002830 nitrogen compounds Chemical class 0.000 title claims abstract description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 239000011159 matrix material Substances 0.000 claims description 29
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- 239000003990 capacitor Substances 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- 150000002825 nitriles Chemical class 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 claims description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims 3
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 150000007960 acetonitrile Chemical class 0.000 claims 1
- 229910003865 HfCl4 Inorganic materials 0.000 abstract description 9
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical group Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 description 19
- 239000007787 solid Substances 0.000 description 17
- 230000008021 deposition Effects 0.000 description 16
- 239000007788 liquid Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 230000014509 gene expression Effects 0.000 description 12
- 239000011261 inert gas Substances 0.000 description 11
- 229910052735 hafnium Inorganic materials 0.000 description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 238000000137 annealing Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 230000000670 limiting effect Effects 0.000 description 5
- 239000002879 Lewis base Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- -1 nitrilo compound Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000000153 supplemental effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 150000007527 lewis bases Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 230000003442 weekly effect Effects 0.000 description 2
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 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
- 239000010409 thin film Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10B—ELECTRONIC MEMORY DEVICES
- H10B12/00—Dynamic random access memory [DRAM] devices
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G27/00—Compounds of hafnium
- C01G27/02—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02181—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G27/00—Compounds of hafnium
- C01G27/04—Halides
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- 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 System
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/3141—Deposition using atomic layer deposition techniques [ALD]
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31645—Deposition of Hafnium oxides, e.g. HfO2
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- H—ELECTRICITY
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28194—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate
Abstract
本发明提供了二氧化铪前体和利用该前体生成二氧化铪层的方法。二氧化铪层前体含有与HfCl4键合的氮化合物。
Description
技术领域
本发明涉及二氧化铪层用前体和利用该前体生成二氧化铪层的一种方法,更具体地说,涉及的二氧化铪层前体能够在低温条件下,以增强电性能和阶梯覆盖率(step coverage)方式,以较快速度沉积;涉及利用该前体生成二氧化铪层的方法,及利用此方法制成的二氧化铪层的电容器和晶体管以及用这些电容器和/或晶体管制成电器元件。
背景技术
在半导体(存储器)元件的栅氧化物层(gate oxide layer)或电容器介电层制作过程中,使用介电材料。介电材料的各种性能大大影响了这些元件的操作性。传统上,氧化硅层已经广泛用于栅氧化物层或电容器的介电层。然而,由于半导体元件是高集成的,对氧化铪层,氧化锆,氧化铝层以及钛酸锶层这些具有高的介电常数的材料的研究已经开展。在这些具有发展远景的介电材料中,二氧化铪(HfO2)被认为是最有可能用于下一代高集成半导体存储元件的,因为它有5.9eV的高带隙能(band gap energy),有20或更大的介电常数,并且在硅和Hf-O之间可以提供良好的界面稳定性。
利用各种传统工艺方法,可沉积二氧化铪层。例如:溅射(sputtering),化学汽相淀积(CVD),或者原子层沉积(ALD)。由于高集成设备需要非常良好的阶梯覆盖,ALD这种方法更有吸引力。然而ALD方法所形成的一定厚度的原子层薄膜是重复沉积的,不能满足所希望的阶梯覆盖要求。
另外,二氧化铪层沉积速度缓慢,因而,在二氧化铪层沉积过程中,作为下电极沉积的硅被氧化成SiO2。众所周知,仅仅用一个二氧化铪层是不能得到介电性能。例如:当用HfCl4作为Hf的来源(最常用)沉积二氧化铪层时,二氧化铪层沉积速度低到0.07nm/周期,尽管理论值可以高达0.11nm/周期或更高。沉积速度低的一个原因被认为是由于分子中相邻Cl原子之间的排斥力,导致单位面积内,HfCl4沉积数量降低。
作为Hf的主要来源的HfCl4室温下是固态,而且在200℃下具有0.1托(torr)的低蒸气压。因此,使用鼓泡法时,每个周期可提供到反应器的HfCl4非常少。所以,当这个Hf源被用于形成三维电容器时,表面面积太大和阶梯覆盖小是不可避免的。
发明内容
因此,本发明提供一种二氧化铪层用前体,它不再具有传统Hf源,HfCl4.所出现的问题。
本发明提供一种使用二氧化铪前体生成二氧化铪层的方法。
本发明提供一种含有用上述方法制成的氧化铪层的存储器用电容器或晶体管,以及包括这种电容器或晶体管的电器元件。
一方面,本发明提供含有与HfCl4.结合的氮化合物的二氧化铪层用前体,这种氮化合物包括有:吡啶,胺,腈。
另一方面,本发明提供生成二氧化铪层的方法,包括:准备含有与HfCl4结合的氮化合物的二氧化铪层用前体溶液;在反应器中吸收二氧化铪层用前体溶液到基体表面;以及向反应器中加入氧化剂来氧化基体表面所吸收的物质,从而在基体表面形成原子二氧化铪层。
另一方面,本发明提供电容器的结构,包括:下电极;在下电极上生成的介电层;和在介电层上形成上电极;其中介电层是利用上述方法在下电极上沉积的。
另一方面,本发明提供晶体管的结构,包括:源电极;漏电极;在源电极和漏电极之间具有导电区(conductive region)的基体;在具有导电区基体上所形成的栅介电层,和在栅介电层上所形成的栅电极;其中栅介电层是通过上述方法沉积在导电区上的。
另一方面,本发明提供一种电子元件,它至少包括利用上述方法生成的电容器结构和晶体管结构之一。优选地,这种电子元件是一种动力随机存取存储元件(DRAM)。
附图说明
通过参考附图对具体实施方案的详述,本发明上述目的和优点将更清楚。
图1说明了传统的二氧化铪前体中原子的相互作用。
图2说明了依据本发明生产的二氧化铪前体中原子的相互作用。
图3是一个包括根据本发明实施例生成的晶体管的存储元件的结构剖面图。
图4和5是存储元件结构的剖面图,每一个都包括有根据本发明另一个实施方案所制成的电容器和晶体管。
图6说明根据本发明生成的二氧化铪前体供给次数与二氧化铪层厚度偏差的关系曲线图。
图7是说明惰性气体清洁时间(purging time)与二氧化铪层厚度偏差的关系曲线图。
图8和9说明了本发明方法生成的二氧化铪层中杂质的浓度。
图10说明了本发明生成的二氧化铪层阶梯覆盖率。
发明详述
根据本发明,使用了一种二氧化铪层用前体,其含有与HfCl4,结合(coordinate)、且起到了路易斯碱作用的氮化合物,这种前体可代替传统铪前体,HfCl4。
当充当路易斯碱的氮基化合物(nitrogen-based compound)与HfCl4结合时,氮基化合物的一对自由电子就会提供到芯金属铪,如图2所示,铪与氯原子之间的结合力减弱。因此,当前体被吸收到基体上,相邻氯原子的排斥力以及铪与氯原子之间的结合力都减小,随之增加了每个周期的铪被氧化的速度,并增加沉积到单位面积上的HfCl4的量。所以,二氧化铪层的沉积速度可改善。由于沉积速度得到改善,下电极暴露在不需要的氧化条件下的时间减少,在下电极上形成较少的氧化物,因而导致其电性能加强。
供给芯金属铪的电子对有助于铪和基体之间相互作用,所以可加强二者之间的结合力。换句话说,生成的二氧化铪层和基体之间的结合力也得到加强。同样的,由于芯金属铪和氯原子之间的结合力减小了,氯原子很容易被氧化剂离解,所以氧与铪的结合容易进行。
根据本发明的二氧化铪前体可以通过充当路易斯碱的氮化合物与HfCl4结合来衍生得到。室温条件下,HfCl4是固态。为了与氮化合物结合,优选室温条件液体HfCl4。例如,当乙腈用作氮化合物时,固态HfCl4分散在乙腈中,室温条件下液体,然后在真空中蒸发。产生的残余物被用为含有与HfCl4结合的氮化合物的二氧化铪前体。这里,加入到氮化合物中的HfCl4浓度为0.01-1M。
根据本发明,当使用室温下非液态氮化合物时,可以使用能溶解或稀释氮化合物的有机溶剂以得到二氧化铪前体。适用的有机溶剂包括,但不限定于,环己烷,四氢呋喃,乙酸正丁酯,丁腈,丙腈,等。这时,优选HfCl4浓度范围为0.01-1M。
根据本发明,适用于二氧化铪前体的含有孤对电子作为路易斯碱的氮化合物是吡啶,胺,或腈。
适用为氮化合物的胺有如下的分子式(1):
NR1R2R3...(1)
其中R1,R2,和R3独立地代表氢,卤素原子,和取代或非取代C1-C10烷基。适用为氮化合物的胺的例子包括,但非限定于,胺,一甲胺,一乙胺,一丙胺,一异丙胺,甲基乙基胺,甲基丙基胺,乙基丙基胺,二甲胺,二乙胺,二丙胺,二异丙胺,二丁胺,等。
适用为氮化合物的腈有如下的分子式(2):
NCR4...(2)
其中R4是取代或非取代C1-C10烷基。适用为氮化合物的腈的例子有,但非限定于,乙腈,异丙腈,丁腈,等。
适用为氮化合物的吡啶有如下的分子式(3):
其中R5,R6,R7,R8,和R9可以分别独立地为取代或非取代C1-C10烷基,氰基,氨基,和羟基。适用为氮化合物的吡啶的例子有,但非限定于,吡啶,乙基吡啶,甲基吡啶,丙基吡啶,吡唑,等。
在上述这些取代基团中,取代或非取代烷基是指直链和支链具有1到10个碳原子,优选1到8个碳原子,更优选1到5个碳原子的基团。这些基团的例子包括:甲基,乙基,正丙基,正丁基,异丁基,仲丁基,叔丁基,戊基,异戊基,己基,辛基等。最优选的是具有1到3个碳原子的低级烷基。这些烷基上至少有一个氢原子可以被卤素原子,羟基,羧基,氰基,胺基等代替。
根据本发明的二氧化铪层前体能用于形成多层结构,其包括二氧化铪层或多成分层。这个二氧化铪层可以用一般方法制成,如CVD,ALD等。
这里将叙述利用ALD形成二氧化铪层方法。开始,根据本发明,将含有与HfCl4结合的氮化合物的二氧化铪层前体溶解于预定的有机溶剂中或用预定的有机溶剂中稀释以获得前体溶液。由于含有与HfCl4结合氮化合物的前体为固态形式,为了得到更好的沉积效果,最好先制备好前体溶液而不是直接将固态前体注入蒸发器中。因此,应用有机溶剂将二氧化铪前体溶解或稀释。适用的有机溶剂有,但非限定于,环己烷,四氢呋喃,乙酸正丁酯,丁腈,丙腈,等。这时,应当控制加入的有机溶剂的量使得前体溶液中的HfCl4浓度范围为0.01-1.0M。
或者,在准备前体溶液时,可以加入适量的固态前体中与HfCl4结合的氮化合物,以加强前体溶液的化学稳定性。例如,当使用乙腈和HfCl4结合得到的固态前体,把固态前体溶解于有机溶剂时,进一步加入适量的乙腈,以提高化学稳定性。这时,应当控制所加入氮化合物的量使前体溶液中HfCl4浓度范围为0.01-1.0M。
然后,加热即将沉积薄膜的基体。将基体送入反应器,温度稳定在预先设定的范围内。优选,基体温度范围为200-500℃,更优选为250-500℃。如果基体温度低于200℃,HfCl4的物理吸附太多以至不能清除。如果基体温度超过500℃,前体在沉积前会分解和蒸发。所以,使用CVD沉积前体而不用ALD。
基体的种类不用限定,都可使用。适用的基体例子包括,聚硅基体,TiN/Si基体,Ru/SiO2/Si基体,和Pt/Ti/SiO2/Si基体。
接着,将惰性气体加入反应器以产生非氧化气氛。氢气,氮气等,都可用作惰性气体。优选,惰性气体的流速为30-500sccm。如果惰性气体的流速超过这个范围,前体的蒸气分压会降低,前体的沉积速度也会下降。
接着,根据本发明,利用蒸发器,将二氧化铪前体蒸发供入反应器以被吸收到基体表面。优选,就前体的稳定性和蒸发的有效性而言,蒸发器的温度控制在180-260℃,更优选,220-240℃范围。优选地,所供前体的流速是0.01-0.3毫升/分钟(cc/min)。如果蒸发器温度低于180℃,部分HfCl4不能蒸发,存留在蒸发器内,导致阻塞蒸发器。如果蒸发器温度高于260℃,部分HfCl4沉积在蒸发器的内壁上。
根据本发明,可以用多种方法而没有限制,将二氧化铪前体送入反应器,例如,可用扩散器(bubbler)或直接喷射的方法。
在直接喷射方法中,用有机溶剂溶解或稀释固态前体制得的二氧化铪前体溶液,以一定浓度经过喷嘴直接供入蒸发器。在直接喷射方法中,前体进入蒸发器是以分时同步法(time-division synchronization)进行。特别是,喷嘴打开一定时间供入前体,然后关闭,停止前体供应。所以前体的消耗减少。或者,可以重复打开和关闭喷嘴。接着,经喷嘴喷入的气溶胶(areozole)被蒸发。这样每个周期供给前体的量将大大增加。利用这个方法提供前体,可以消除HfCl4高沸点问题。
如上所述,根据本发明,二氧化铪前体被吸收到基体表面后,未被吸收多余的前体用惰性气体清除。由沉积装置可改变惰性气体的流速。优选惰性气体的流速为100-500sccm。优选反应器的工作压力控制范围是0.1-3torr。根据需要,惰性气体清除的过程可以省略。
接着,被吸收到基体表面的二氧化铪前体,与氮化合物结合的HfCl4,通过注射一种氧化性气体使其氧化,以原子层的形式生成二氧化铪层。水蒸气,O2,N2O气,或等离子体增强的O2或O3气,可被作为氧化性气体使用。氧化性气体流速可以不同。然而,优选氧化性气体流速100-300sccm。
在供给氧化剂之前或之后或同时,可另加入反应的活化剂。优选反应活化剂包括:吡啶,乙腈,胺类。在前体氧化过程中,反应活化剂通过减弱Hf-Cl键的结合,使前体氧化更容易,提高沉积效率。
上述利用惰性气体清洗反应器,吸收二氧化铪前体到基体上,用惰性气体清除多余的前体,并氧化二氧化铪前体的过程能重复进行,直到获得所期望厚度二氧化铪层。优选二氧化铪层厚度为20-200。介电常数大约为25。
二氧化铪层形成随后是高温退火,进一步晶化二氧化铪以获得增强的介电性能。优选高温退火是在氧化气氛或真空下,温度500-900℃,进行1-30分钟。利用水蒸气,O2,N2O气,或等离子体增强的O2或O3气,得到氧化气氛。优选,真空程度控制大约0.01-10torr,更优选,大约35mtorr。
随后,将介绍由CVD制二氧化铪层的方法。
开始,在反应器中建立氧化气氛。用氧化性气体,如水蒸气,O2,N2O气,或等离子体增强的O2或O3气可建立氧化气氖。根据沉积设备,改变氧化性气体的流速。然而100-500sccm的氧化性气体流速是优选的。
接着,即将在其上形成二氧化铪层的基体的温度应稳定在预定范围内。优选基体温度范围200-500℃。如果基体温度超过这个范围,在上述ALD方法中出现的问题也能在此出现。与上述ALD方法同样种类的基体可以使用。
二氧化铪层前体在氧化气氖里被供入反应器以将HfO2层沉积到基体上。二氧化铪前体的组成,供入二氧化铪前体的方法,以及其他的条件,可与上述ALD方法相同或相近。
与上述ALD方法相近,二氧化铪层形成随后的工艺是与上述方法相同的条件下,高温退火,以使二氧化铪的晶化容易进行。
根据本发明,二氧化铪前体能用于电器元件的制作中。“电器元件”这个词意思是晶体管,电容器,二级管,电阻器,开关,发光二极管,激光器,或互连结构。
举例,电容器的结构是在上、下电极之间形成介电层,其中这个介电层是根据上述方法由二氧化铪层形成。任何材料都可用作上下电极而没有限制。例如,Si,TiN,和Pt族元素就可用作上、下电极材料。比如,Pt族元素由铷(Ru),锇(Os),铱(Ir),铂(Pt)组成,可使用至少一种Pt族元素作为电极材料。
举例,叙述电容器结构的制作方法。开始,在Pt族元素形成的下电极表面,根据本发明,利用ALD或CVD法,用二氧化铪前体生成二氧化铪层。
然后,在二氧化铪层上形成上电极,接着高温退火。如上所述,高温退火的进行是为了进一步晶化二氧化铪和加强介电性。优选高温退火在氧化气氛,非活性,或真空下,温度500-900℃,进行1-30分钟。高温退火在真空下进行时,真空度控制在0.01-10torr范围,优选约35mtorr。
高温退火之后是补充热处理工艺。当在二氧化铪介电层上下层形成的上、下电极难以氧化时,进行补充热处理工艺,为了使补充氧气进入二氧化铪层和每一个上下电极的界面之间。补充热处理工艺操作是在真空非活性气氛,或空气条件下进行10-60分钟,温度低于1000℃,优选450-750℃。
根据本发明,二氧化铪层能用于制作晶体管的栅介电层。尤其是,在基体的源电极和漏电极之间的导电区上,用如上述方法所述,将二氧化铪层沉积为栅介电层。接着,在栅介电层上形成栅电极,得到晶体管。
根据这个方法形成的晶体管的例子如图3所示。参考图3,晶体管10结构为:在硅基体11的源电极15和漏电极15b之间的导电区上排有栅电极13,在栅电极14下形成栅介电层14。在这个结构里,栅介电层14是由本发明的上述方法制成的二氧化铪层形成的。在栅电极13和栅介电层14的两侧形成起到保护作用的隔板17。图3里的数字16表示的是非活性区。
根据如上所述本发明方法制成的电容器和/或晶体管可用于各种电子元件,如动力随机存取存储元件(DRAM)。
图4和5是使用了根据本发明方法制成的电容器和晶体管的存储元件结构剖面图。在图4和5中,参考数字10表示晶体管,参考数字11表示硅基体,参考数字12表示导电区,参考数字13表示栅电极,参考数字14表示栅介电层,参考数字15a表示源电极,参考数字15b表示漏电极,参考数字16表示非活性区,参考数字17表示隔板,参考数字18表示下电极,参考数字19表示由本发明的二氧化铪层形成的介电层,参考数字20表示上电极,参考数字21表示一个电容,参考数字22表示底层结构(underlyingstructure)。
下面的实施例对本发明进行了详细叙述。这些实施例只是说明而非限定发明的范围。
实施例1
在100mL乙腈中溶解6.406g固体HfCl4以获得0.2-M溶液。在50℃真空下,蒸发溶液获得7.254g固体残渣。将固体残渣溶解于100mL四氢呋喃中,得到液态二氧化铪前体。
根据对残渣原子分析的结果,检测到碳和氮原子的摩尔比为3.4∶1.1。由此清楚地表明乙腈与HfCl4化学键合。
实施例2
在100mL吡啶中溶解6.406g固体HfCl4,以获得0.2-M溶液。在50℃真空下,蒸发溶液获得7.023g固体残渣。将固体残渣溶解于100mL丙腈中,得到液态二氧化铪前体。
实施例3
在100mL乙腈中溶解6.406g固体HfCl4以获得0.2-M溶液。在50℃真空下,蒸发溶液获得7.254g固体残渣。将固体残渣溶解于100mL四氢呋喃中,得到液态二氧化铪前体。
实施例4
在100mL乙腈中溶解6.406g固体HfCl4以获得0.2-M溶液。在50℃真空下,蒸发溶液获得7.254g固体残渣。将固体残渣溶解于100mL乙腈中,得到液态二氧化铪前体。
实施例5
将实施例3得到的液态二氧化铪前体经过喷嘴喷入ALD用蒸发器中,产生的气溶胶被蒸发。此时经分时同步法提供二氧化铪层前体0.01秒。当载气以200sccm速度流入反应器时,前体蒸气被转入反应器,并被吸收在多Si/SiO2/Si基体上。这时反应器维持在200℃和0.17torr。用流速200sccm的氮气流动3秒钟,将未反应的前体从反应器中除出。将作为氧化剂的水蒸气,在室温、在产生水蒸气的压力下,向反应器注入3秒钟,氧化已被吸收的前体并形成二氧化铪层。反应器用200sccm的氮气再次清洗。接着重复上述步骤,直到所期望厚度的二氧化铪层被沉积。
在实验中,前体的注入量是通过提高前体的脉冲次数得到增加。结果如图6。正如图6所示,即使增加了前体被注入的用量,前体的沉积速度仍然不变,满足了ALD的要求。
图7是清洁时间与沉积速度变化关系曲线。当前体被清洗3秒钟或更长时间,由于前体和水蒸气没有接触,在前体和作为氧化剂的水蒸气之间没有反应发生。纯前体的沉积速度为每周期0.2nm或更大。
实施例6
以实施例5相同方式,生成二氧化铪层,不同的是采用实施例2方法准备的液态二氧化铪前体,代替以实施例3的准备方法得到的二氧化铪前体。测量二氧化铪层中杂质的浓度。结果见图8和9。
如图8和9所示,在270和400℃沉积温度下,检测到的氯和碳均少于1%。很明显,使用本发明的前体可以形成高质量的二氧化铪层。沉积速度如实施例5,为每周期0.2nm或更高。
实施例7
以与实施例5相同方式生成二氧化铪层,不同的是采用实施例4方法准备的液态二氧化铪前体,代替以实施例3的准备方法得到的二氧化铪前体。用二氧化铪层可以测量阶梯覆盖率,结果如图10。
如图10所示,根据本发明,液态前体经喷嘴喷射形成二氧化铪层时,阶梯覆盖率可提高到85%或更高,而传统的鼓泡法的阶梯覆盖率仅有30%或更低,
实施例8
利用实施例4制备好的液态二氧化铪前体,在300℃下,在多Si/SiO2/Si基体上生成二氧化铪层,接着空气条件下,750℃退火10分钟。通过溅射在二氧化铪层上形成Pt电极,测量其电性能。结果,可以得到在1V条件下,10-7A/cm2或更低的电特性,这正是电子元件的要求。
如上所述,本发明提供了在低温下高速度沉积的二氧化铪前体,并提供了改善的电特性和阶梯覆盖率。本发明提供了使用该前体生成二氧化铪层的方法,含有利用该方法生成的二氧化铪层的电容器或晶体管,和含有电容器和/或晶体管的电子元件。
尽管参考优选的实施例对本发明进行了具体的说明和叙述,本领域的普通技术人员应当懂得,在不脱离本发明的精神和所附权利要求所限定的范围下,在形式和细节上可能作出各种变化。
Claims (13)
1.二氧化铪层用前体,其中该前体包含与HfCl4键合的氮化合物,其中氮化合物包括具有如下分子式的腈类:
NCR4
其中R4是取代或非取代C1-C10烷基。
2.如权利要求1的二氧化铪前体,其中腈类包括:乙腈,异丙腈,丁腈,并且氮化合物含有至少一种前述的腈。
4.如权利要求3的二氧化铪前体,其中吡啶类包括:吡啶,乙基吡啶,甲基吡啶,丙基吡啶,吡唑,并且氮化合物含有至少一种前述吡啶。
5.生成二氧化铪层的方法,包括:
制备含有与HfCl4键合的氮化合物的二氧化铪前体溶液;
在反应器中吸收二氧化铪前体溶液到基体的表面,并且
通过向反应器内提供氧化剂氧化吸收到基体表面的前体,从而在基体表面形成二氧化铪层。
6.如权利要求5的方法,还包括在提供氧化剂之前或之后或同时,提供反应活化剂。
7.如权利要求5的方法,其中氧化剂为水蒸气,氧气,N2O气,或等离子体加强的氧气或O3气。
8.如权利要求6的方法,其中反应活化剂包括吡啶类,乙腈类,和胺类。
9.如权利要求5的方法,其中二氧化铪前体溶液含有至少一种选自四氢呋喃,乙酸正丁酯,环己烷,丙腈,和丁腈的有机溶剂。
10.如权利要求5的方法,其中二氧化铪前体溶液经过蒸发器被供入反应器。
11.如权利要求5的方法,在一定的时间间隔内,通过打开和关闭蒸发器的喷嘴,提供二氧化铪前体溶液。
12.电容器的结构,包括:
下电极;
在下电极上形成的介电层;和
在介电层上形成的上电极;
其中所述的介电层是通过权利要求5的方法形成的二氧化铪层。
13.晶体管结构,包括:
源电极
漏电极
在源电极和漏电极之间具有导电区的基体;
在基体的导电区上形成的栅介电层;和
在栅介电层上形成的栅电极
其中所述的栅介电层是通过权利要求5的方法形成的二氧化铪层。
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US20060118891A1 (en) | 2006-06-08 |
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KR100513719B1 (ko) | 2005-09-07 |
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US7399716B2 (en) | 2008-07-15 |
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