CN102473603B - 原子层沉积用高浓度水脉冲 - Google Patents
原子层沉积用高浓度水脉冲 Download PDFInfo
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- CN102473603B CN102473603B CN201080035028.9A CN201080035028A CN102473603B CN 102473603 B CN102473603 B CN 102473603B CN 201080035028 A CN201080035028 A CN 201080035028A CN 102473603 B CN102473603 B CN 102473603B
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- reaction compartment
- reactant
- water
- dielectric oxide
- hafnium
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 238000000231 atomic layer deposition Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 106
- 238000000034 method Methods 0.000 claims abstract description 88
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000004065 semiconductor Substances 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims description 94
- 230000008021 deposition Effects 0.000 claims description 41
- 239000012808 vapor phase Substances 0.000 claims description 25
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 19
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 19
- 229910052735 hafnium Inorganic materials 0.000 claims description 17
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- -1 gold-plating Chemical compound 0.000 claims description 11
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 5
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052689 Holmium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052773 Promethium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 229910052775 Thulium Inorganic materials 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 5
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 5
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 5
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 5
- 238000007747 plating Methods 0.000 claims description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 5
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 5
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- NRVQHRXZCZWHMD-UHFFFAOYSA-N [Si](=O)=O.[Hf] Chemical compound [Si](=O)=O.[Hf] NRVQHRXZCZWHMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 3
- 229910052712 strontium Inorganic materials 0.000 claims 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 239000003990 capacitor Substances 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 38
- 239000012159 carrier gas Substances 0.000 description 22
- 239000002356 single layer Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000006872 improvement Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 10
- 238000003809 water extraction Methods 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 239000000428 dust Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002052 molecular layer Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001805 chlorine compounds Chemical group 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003877 atomic layer epitaxy Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000541 pulsatile effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000007115 recruitment Effects 0.000 description 1
- 230000026267 regulation of growth Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008400 supply water Substances 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
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 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
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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]
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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- C—CHEMISTRY; METALLURGY
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Abstract
本文提供通过原子层沉积形成含氧薄膜的方法。所述含氧薄膜可以通过将向反应空间中的基板提供浓度较高的水脉冲、较高的反应空间中的水分压及/或较高水流速而沉积。含氧薄膜可以例如用作晶体管、电容器、集成电路及其它半导体应用中的介电氧化物。
Description
技术领域
本申请通常涉及使用水作为反应物,通过原子层沉积来形成含氧薄膜的方法。此类薄膜可例如用于集成电路中。
背景技术
原子层沉积(ALD)是一种自限式方法(self-limitingprocess),由此反应物的交替脉冲使基板表面饱和,而且每一周期留下不超过一个材料单层。沉积条件及反应物经过选择,应能确保自饱和反应(self-saturatingreaction),使得在一次脉冲中的吸附层产生表面终止状态(surfacetermination),表面终止状态表示其不与同一脉冲的气相反应物反应。接下来的不同反应物脉冲与先前的终止状态反应,以使沉积能继续进行。因此,每一交替脉冲周期通常留下少于约1个或不超过约1个所需材料分子层。ALD型方法的原理已例如由T.Suntola呈现于例如HandbookofCrystalGrowth3,ThinFilmsandEpitaxy,第B部分:GrowthMechanismsandDynamics,第14章,AtomicLayerEpitaxy,第601-663页,ElsevierScienceB.V.1994中,所述文献的公开内容以引用的方式并入本文中。已经针对ALD提出了允许调节生长速率的变更。然而,为了提供高保形性及厚度均一性,此等反应仍或多或少为自饱和反应。
发明内容
根据一些实施方案,提供通过原子层沉积在反应空间中的基板上形成含氧薄膜的方法。所述方法包含沉积周期,包括:向反应空间提供第一反应物的气相反应物脉冲,由此其在基板表面上形成不超过第一反应物单层;自反应空间中去除过量的第一反应物;向所述反应空间提供含水的第二反应物的气相反应物脉冲,使得所述反应空间中的水分压高于约100毫托(mTorr);以及自所述反应空间去除过量的第二反应物及任何反应副产物。
根据一些实施方案,提供通过原子层沉积在反应空间中的基板上形成含氧薄膜的方法。所述方法包括:向反应空间交替且连续地提供包括含氯前体的气相反应物脉冲及含水的气相反应物脉冲;其中重复所述气相反应物脉冲,直至获得具有所需厚度的薄膜,其中提供含水气相反应物脉冲,使得反应空间中的水分压高于约200毫托。
根据一些实施方案,提供通过原子层沉积在反应空间中的基板上形成薄膜的方法。所述方法包括:使基板与包括第一前体的气相反应物脉冲及含水的气相反应物脉冲交替且连续地接触,其中提供水,使得反应空间中的水分压高于约250毫托;及重复所述交替且连续的脉冲,直至获得具有所需厚度的薄膜。
为了概述本发明及所获得的优于先前技术的一些优点,上文已经描述了本发明的某些目的及优点。当然,应了解,根据本发明的任一特定实施方案,未必能实现所有所述目的或优点。因此,例如本领域技术人员将认识到,实施或进行本发明的方式应能实现或优化本文所教示的一个优点或一组优点,无需实现本文所教示或提出的其它目的或优点。
所有此等实施方案都将在本文所公开的本发明的范围内。自以下参照随附图式的较优选实施方案的详细描述,本发明的此等及其它实施方案对本领域技术人员显而易见,本发明不限于所公开的任何特定较优选实施方案。
附图说明
图1是大体上说明根据一些实施方案形成含氧薄膜的方法的流程图。
图2是说明通过ALD法,使用加热至不同温度的氯化铪及水沉积的二氧化铪膜的膜厚度的曲线图。
图3是说明通过ALD法,在75℃的容器温度下,使用氯化铪及水沉积的二氧化铪膜的中心膜厚度与沉积周期数的间关系的图。
图4是说明通过ALD法,在75℃的容器温度下,使用水沉积的二氧化铪膜的铪原子表面密度与沉积周期数的间关系的图。
图5是说明通过ALD法,在75℃的容器温度下使用水沉积的二氧化铪膜的隧道电压与等效氧化层厚度(EOT)的间关系的图。
图6是通过ALD法,在各种源温度下使用氯化铪及水沉积的二氧化铪膜中氯及硅含量的二次离子质谱仪(SIMS)影像。
具体实施方式
可以利用原子层沉积(ALD)型方法,使用本文所述的方法及装置,在基板上沉积含氧薄膜。尽管在集成电路、介电氧化物、电容器、晶体管或其它半导体组件的一部分中形成含氧薄膜的情形中说明本文中所公开的原理及优点,但本领域技术人员将容易了解所述原理及优点适用于可使用含氧薄膜的各种其它情形。
原子层沉积(ALD)
ALD型方法是基于受到控制的自限式表面反应。通过将前体交替且连续地馈入反应空间中,可以避免气相反应。反应空间中气相反应物彼此分离是例如通过在反应物脉冲的间自反应空间去除过量的反应物及/或反应副产物实现。
由于ALD方法的自限特性允许更好地控制膜生长,故在一些应用中,ALD方法优于化学气相沉积方法(CVD)。ALD方法也可制造出均一性高于一些CVD方法的薄膜。
简言之,在ALD方法中,将基板装载至反应空间中,并且一般在较低压力下,加热至适合的沉积温度。沉积温度通常保持低于反应物的热解温度,但达到足够高的水平,以避免反应物缩合,并为所需表面反应提供活化能。当然,任何指定ALD反应的适当温度限度将视表面终止状态及所涉及的反应物的种类而定。此处,温度较优选低于约600℃,更优选低于约500℃,甚至更优选低于400℃,且最优选低于约300℃。下文将提供一些具体实施方案的特定沉积温度。
将第一反应物以气相脉冲的形式传输或脉冲输送至反应空间中,并与基板表面接触。较优选选择条件使得以自限方式将仅约一个第一反应物单层吸附至基板表面上。过量的第一反应物及反应副产物(若存在的话)是诸如通过用惰性气体冲洗而自反应空间去除。本领域技术人员易于根据特定情形确定适合的脉冲时间。
冲洗反应空间意谓,诸如通过用真空泵抽空反应空间,及/或通过用诸如氩气或氮气的惰性气体置换反应器内部的气体,自反应空间中去除气相前体及/或气相副产物。典型的冲洗时间为约0.05秒至20秒,更优选在约0.25秒与10秒的间,且更优选在约0.5秒与2秒的间。然而,必要时,诸如在需要高度保形步阶覆盖(conformalstepcoverage)极高纵横比结构或其它具有复杂表面形态的结构时,可以利用其它冲洗时间。另外,由于体积及表面积的增加,分批式ALD反应器可以利用较长的冲洗时间。本领域技术人员可根据特定情形确定冲洗时间。
将第二气态反应物脉冲输送至反应空间中,其中所述反应物与结合至表面的第一反应物反应。较优选藉助于惰性气体冲洗及/或抽空,自反应空间中去除过量的第二反应物及表面反应的气态副产物。重复脉冲输送及冲洗步骤,直至已经在基板上形成具有所需厚度的薄膜,其中每一周期通常会留下小于一个或仅一个分子单层。
如上文所述,每一周期的每一脉冲或阶段较优选为自限式的。在每一阶段供应过量的反应物,以使易受影响的结构表面理想地饱和。表面饱和将确保反应物占据所有可用的反应位点(例如受实际尺寸(physicalsize)或“位阻(sterichindrance)”限制),由此确保优良的步阶覆盖。实务上,难以达成完全表面饱和。
需要以较少周期数及较短周期时间形成连续膜。较长的反应物脉冲可以改良每一周期的步阶覆盖,且每一周期产生较高生长速率。然而,较长的脉冲时间会使周期时间及总体晶圆方法时间增加量大于在较长脉冲时间下所产生的每一周期的膜厚度生长的增益。因此,需要优化脉冲时间及反应条件,使得在较少周期数(其中每一周期优化成相对较短的持续时间)后获得质量较高的连续膜。结果,无需较长脉冲长度,每一周期中的少量生长增益及沉积膜的质量可明显减少晶圆方法时间及成本。
在本文所述的一些实施方案中,描述一种方法,其将增加反应器中水的浓度,由此在不使用较长水脉冲长度的情况下,引起水分子表面饱和度的改良以及膜生长的增加,同时还展现ALD方法特有的自限特性。先前认为反应器中的高浓度水难以有效除去且几乎不可能有效除去,且先前脉冲留在反应器中的残余水可能会破坏ALD方法的自限特性。在本发明方法中,所得金属氧化物膜的电性质远远胜过低剂量水脉冲,包含在同一等效氧化层厚度(EOT)下较少的漏电流。此等改良的结果也可利用较短的反应物脉冲获得。
图1是大体上说明根据一个实施方案形成含氧薄膜的方法的流程图。根据较优选实施方案,通过包括多个沉积周期的ALD型方法100,在反应空间中的基板上形成含氧薄膜,各沉积周期包括:
向反应空间提供第一反应物的气相反应物脉冲,由此其在基板表面上形成不超过第一反应物单层;
自反应空间去除过量的第一反应物;
向反应空间提供含水的第二反应物的气相反应物脉冲;及
自反应空间去除过量的第二反应物及任何反应副产物;
这可称为氧化物沉积周期(oxidedepositioncycle)。重复所述周期,直至获得具有所需厚度及组成的薄膜。
首先,将包括第一反应物的气相反应物脉冲提供至基板及反应空间110。
第一反应物可例如包括(但不限于)选自由以下构成的组的元素:镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钷(Pm)、钐(Sm)、铒(Er)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铥(Tm)、镱(Yb)、钪(Sc)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锆(Zn)、钇(Y)、锆(Zr)、铌(Nb)、钼(Mo)、鎝(Tc)、钌(Ru)、铑(Rh)、钯(Pd)、银(Ag)、镉(Cd)、镏(Lu)、铪(Hf)、钽(Ta)、钨(W)、铼(Re)、锇(Os)、铱(Ir)、铂(Pt)、金(Au)、汞(Hg)、锑(Sb)、碲(Te)、铍(Be)、铋(Bi)、硼(B)、碳(C)、铝(Al)、硅(Si)、磷(P)、铟(In)、镓(Ga)、锗(Ge)及锡(Sn)。第一反应物较优选包括钛、铝、铪、硅及锆中一者或多者。在一些实施方案中,第一反应物包括铪且沉积二氧化铪薄膜。
在一些实施方案中,可以沉积包括二氧化铪或二氧化锆的膜。在一些实施方案中,二氧化铪膜或二氧化锆膜可以掺杂有稀土元素,例如镧、铈、镨、钕、钷、钐、铒、钆、铽、镝、钬、铥、镱、镏。在一些实施方案中,沉积膜包括HfTiO2、ErHfO2、LaZrO、SrBaTiO3及SrTiO3。
在一些实施方案中,沉积方法可以水脉冲开始及结束。举例而言,在初始的水脉冲后,可以执行包括第一反应物脉冲及水脉冲的多个沉积周期,以沉积具有所需厚度的膜。
在一些实施方案中,第一反应物较优选为卤化物。在一些实施方案中,卤化物是氯化合物(chlorinecompound)且包括至少一个氯原子。在一些实施方案中,使用金属卤化物,例如具有式MXn的化合物,其中M是金属,X是卤素,且n等于M的价态,例如当M是钛时,所述金属卤化物为氯化钛(TiCl4)、溴化钛(TiBr4)及碘化钛(TiI4)。在一些较优选实施方案中,金属卤化物前体选自氯化铝(AlCl3)、氯化铪(HfCl4)、氯化硅(SiCl4)及氯化锆(ZrCl4)。
在一些实施方案中,第一反应物包括一或多种选自由以下构成的组的配位体:经取代或未经取代的烷基-、烷基酰胺-、醇化物-、脒基-、芳基-、β二酮基-、酰亚胺基-酰胺基-及环戊二烯基化合物。在一些实施方案中,金属有机化合物选自由以下构成的组:三甲基铝、四(乙基甲基)胺基铪、四(二甲基)胺基铪、四(二乙基)胺基铪、四(乙基甲基)胺基锆、四(二甲基)胺基锆及四(二乙基)胺基锆。
第一反应物较优选在基板上仅形成约单一分子层。必要时,可自反应空间冲洗或去除任何过量的反应物120。在一些实施方案中,冲洗步骤可以包括停止第一反应物的流动,同时仍继续诸如氮气或氩气的惰性载气的流动。
接着,将含水(H2O)的第二反应物的气相反应物脉冲提供至基板及反应空间130。在一些实施方案中,所提供的水可以是水与诸如氮气或氩气的不活泼气体(inactivegas)的混合物。
水是一种极性分子,通常会展现强氢键结合力。此等物理性质导致在水脉冲后反应空间中的水缓慢脱气的顾虑。ALD方法设计成避免或最小化CVD型气相反应。未吸附于基板表面上且在第一反应物脉冲期间仍保留在反应空间中的残余水可产生气相或CVD型反应,这可能破坏ALD方法的自限特性。由于此等反应可能在基板表面上引起不均匀生长,故其也为不合需要的。
意外的是,增加反应空间中的水分压、增加水流入反应空间的流速或增加水容器中的蒸汽压,不会引起沉积薄膜质量方面的问题。令人惊讶的是,沉积薄膜展现较低的杂质含量、改良的电性质、较高的生长速率及/或较优选的成核作用。
在一些实施方案中,将水提供至反应空间中,使得反应空间中的水分压高于约10毫托,即反应空间中的典型水分压。甚至更优选地,在方法期间,水浓度或水分压比反应空间中典型水浓度或分压高一个数量级。
在一些实施方案中,可通过控制水源温度、载气流速、水流速、水源压力等,调节反应空间中的水分压。
在一些实施方案中,将水提供至反应空间,使得反应空间中的水分压高于约100毫托。在一些实施方案中,将水提供至反应空间,使得反应空间中的水分压高于约200毫托或约250毫托。在一些实施方案中,在甚至更高的分压下,例如在高于500毫托的分压下,将水提供至反应空间。在一些实施方案中,反应空间中的水分压高于约1000毫托,且在一些情况下,高于约1500毫托。在一些实施方案中,反应空间中的水分压高于约2000毫托,且在一些实施方案中,高于约2500毫托。
在一些实施方案中,水是由温度保持高于室温的水源容器供应。水源容器中的水温较优选高于约37℃,更优选高于约50℃,且最优选高于约75℃。使水源容器温度保持高于室温可以产生较高水蒸气压力。举例而言,在约50℃下,水的蒸汽压为约92托。在一些实施方案中,控制水源容器的条件,使得以高于约500标准毫升/分钟(sccm)的流速将水供应至反应空间。
每一氧化物沉积周期通常仅形成约一个氧化物分子层。必要时,可自反应空间去除任何过量的反应副产物或水140。在一些实施方案中,冲洗步骤可以包括停止水的流动,同时仍继续诸如氮气或氩气的惰性载气的流动。
通常重复所述氧化物沉积周期预定次数150,以形成具有所需厚度的氧化层。在一些实施方案中,通过多个沉积周期形成多个氧化物分子层。在其它实施方案中,形成一个或不到一个金属氧化物分子层。
去除过量反应物可以包含抽空反应空间中的一些内含物,或用氦气、氮气或任何其它惰性气体冲洗反应空间。在一些实施方案中,冲洗可包括切断反应气体的流动,同时使惰性载气继续流到反应空间。
在标准条件(室温及大气压)下,ALD型方法中所用的前体或反应物可以是固态、液态或气态物质,只要在将所述前体或反应物传输至反应空间中并与基板表面接触之前,其为气相即可。将气化的前体或反应物“脉冲输送(pulsing)”至基板上意谓,在有限时段内,将所述前体或反应物蒸气传输至反应空间中。通常,脉冲时间为约0.05秒至10秒。然而,视基板类型及其表面积而定,脉冲时间甚至可以多于10秒。
对于单晶圆ALD反应器中的300毫米晶圆而言,较优选脉冲输送第一反应物0.05秒至10秒,更优选0.1秒至5秒,且最优选约0.3秒至3.0秒。较优选将含水的第二反应物脉冲输送约0.05秒至10秒,更优选0.1秒至5秒,甚至更优选约0.2秒至3.0秒,且最优选约0.1秒至0.5秒。然而,在一些情况下,脉冲时间可达约数分钟。最优选的脉冲时间可由本领域技术人员根据特定情形容易地确定。
反应物的质量流速也可以由本领域技术人员确定。在一个实施方案中,对于在300毫米晶圆上进行沉积,第一反应物的流速较优选(但不限于)在约1标准毫升/分钟与10,000标准毫升/分钟之间,更优选在约100标准毫升/分钟与500标准毫升/分钟之间。第一反应物的质量流速通常低于含水的第二反应物的质量流速,而后者的质量流速通常在(但不限于)约10标准毫升/分钟与10,000标准毫升/分钟之间。
通常,使水流至反应空间的流速最小,以避免在下一次气相反应物脉冲期间发生水脱气,这可能导致不合需要的CVD反应。对于此项技术中已知的ALD方法而言,水流至反应空间的流速通常为约15标准毫升/分钟或低于15标准毫升/分钟。对于大部分制造工具,典型水流速为约10至100标准毫升/分钟。
在一些实施方案中,水流至反应空间的流速明显大于此项技术中已知的方法。水流至反应空间的流速较优选高于约100标准毫升/分钟。水流至反应空间的流速更优选高于约500标准毫升/分钟。甚至更优选地,水的流速高于约750标准毫升/分钟。水流速最优选高于1000标准毫升/分钟。在一些实施方案中,水流速高于2000标准毫升/分钟或甚至高于2500标准毫升/分钟。水流速对应于水的质量流量,并且排除任何载气流量。
反应空间中的压力通常为约0.01毫巴(mbar)(0.0075托)至约20毫巴(15托),更优选为约0.5托至约5托。然而,在一些情况下,压力将会高于或低于此范围,此可由本领域技术人员容易地确定。
在开始膜沉积之前,通常将基板加热至适合的生长温度。含氧薄膜的生长温度较优选低于约600℃,更优选低于约500℃,甚至更优选低于约400℃,且最优选低于约300℃。在一些实施方案中,基板的生长温度较优选为250℃至300℃。在一些实施方案中,基板温度较优选低于约250℃,且更优选低于约200℃。在一些实施方案中,提供及去除步骤期间的基板温度可以低于100℃,并且低至室温或约15℃至25℃。
可以重复沉积周期预定次数,或直至达到所需厚度。薄膜厚度较优选薄至数埃且其厚度更优选在约3埃与200纳米之间。
在一些实施方案中,沉积时,薄膜为结晶。在一些实施方案中,沉积时,薄膜为无定形的。在一些实施方案中,可以将基板退火以增加薄膜的结晶度。
在一些实施方案中,第一反应物的每次脉冲的单层覆盖率大于约20%。可以使用卢瑟福背散射光谱(RutherfordBackscatteringSpectroscopy,RBS)先测定每一周期的表面覆盖率。随后,可以通过用每一周期的RBS覆盖率除以含第一反应物的氧化层的容积无定形密度(bulkamorphousdensity),计算出单层覆盖率。第一反应物的每次脉冲的单层覆盖率较优选大于约21%,且甚至更优选大于22%。
本文所述的方法可以提供许多优于此项技术中已知的方法的优势。
本文所述方法可以改良膜成核作用。膜成核作用的改良可以增加每一周期的单层覆盖率。膜成核作用的改良以及每一周期的单层覆盖率的增加可以使每一周期具有较高生长速率。举例而言,每一周期的单层覆盖率的增加使ALD膜在较少周期内“闭合(close)”(以目标类型的连续ALD膜完全覆盖下伏材料(underlyingmaterial))。膜闭合的改良可以使EOT缩放(EOTscaling)改良,例如当EOT因在较少周期内形成连续ALD膜而减小时,仍保持泄漏(leakage)与EOT线的关系。
本文所述的方法可以制造出质量较高的薄膜,对于指定厚度的沉积薄膜,其可以展现改良的物理缩放(physicalscaling)、改良的泄漏效能及较小的EOT。此外,在各实施例中所用温度下,未观察到不利的颗粒碰撞。
本文所述的方法也可制造出具有较少杂质的薄膜,尤其当使用含氯化物的前体时制造出具有较少氯杂质的薄膜。
本文所述的方法也可使每次脉冲的反应物饱和度改良,而无需较长的脉冲时间。通过增加每一周期的生长速率,而不需搭配增加每一周期时间长度,每一晶圆的方法时间及成本得以降低。
水传递
可以通过多种方法将水提供至反应空间。通常,在室温及低分压下,将水连同载气一起供应至反应空间。根据本文所述的方法,通过各种修改,可以在较高反应器分压下及/或以较大流速,将水提供至反应空间。
在一些实施方案中,可以在固源烘箱(solidsourceoven)中加热水,并将其提供至反应空间。举例而言,颁予Shero等人的美国专利第7,122,085号公开了可用于本发明方法中的固源烘箱的配置。美国专利第7,122,085号中有关固源烘箱配置的公开内容以引用的方式并入本文中。
在一些实施方案中,可通过蒸汽发生器或直接液体注入(directliquidinjector,DLI)系统,将水供应至反应空间。高纯度蒸汽发生器及直接液体注入系统的商品实施例包括由RASIRCTM制造的商品。例如,由RASIRCTM制造的高纯度蒸汽发生系统。在一些实施方案中,蒸汽发生器、DLI系统或其它RASIRCTM系统可经过改变以产生所需的水流速条件。
水源容器
颁予Shero等人的美国专利公开案第2005/0000428号公开了多种反应物源容器。美国专利公开案第2005/0000428号中有关反应物源容器的公开内容以引用的方式并入本文中。在一些实施方案中,水源容器可包括美国专利公开案第2005/0000428号中公开的任何反应物容器。
在一些实施方案中,将水源容器加热至高于约37℃的温度。在一些实施方案中,可以使用较高蒸气压的水,从而以所需流速供应水及/或在反应器中达到所需水分压。在一些实施方案中,可以不藉助于载气将水供应至反应器中。
在一个实施方案中,可以颠倒帕耳帖(Peltier)组件或热电冷却器的操作,以使其可用于加热水源容器。
在一些实施方案中,水脉冲可以藉助于载气(诸如氮气)实现。在一些实施方案中,可以调整载气的流速以在反应器中达到所需水分压。
在一些实施方案中,载气可流过或鼓泡通过水源容器及其内含物。使载气流过水可以在载气流中夹带水及水蒸气。随后,可以使载气及水流至反应空间。在一些实施方案中,可以通过使载气流过水源容器的内含物,将水提供至反应空间。
在其它实施方案中,载气可流经水源容器的出口。载气流经水源容器的出口可以使水及水蒸气自水源容器流出并与载气混合。随后,可以将载气及水提供至反应空间。在一些实施方案中,可以通过使载气流经水源容器的出口,将水提供至反应空间。
在一些实施方案中,可以将水源容器加热至较高温度,例如高于约55℃的温度。在一些实施方案中,将水源容器加热至高于约65℃。在一些实施方案中,将水源容器加热至高于约75℃。较高温度将使水源容器中水的蒸气压升高。较高水压可以产生较高水流速及/或使反应空间具有较高水分压。可以通过使流量控制阀(flowcontrolvalve)节流、在水供应管线中使用限流孔(restrictiveorifice)、使用另一类流量控制阀,或此项技术中已知的控制蒸气流速的任何其它方法来控制水的流速。
在一些实施方案中,控制水流至反应空间的流速,使得反应空间中的分压高于约200毫托或约250毫托。在一些实施方案中,在甚至更高的分压下,例如在高于500毫托的分压下,将水提供至反应空间。在一些实施方案中,反应空间中的水分压高于约1000毫托,且在一些情况下,高于约1500毫托。在一些实施方案中,反应空间中的水分压高于约2000毫托,且在一些实施方案中,高于约2500毫托。
在一些实施方案中,水源容器中水的蒸气压为约92托或更高。在一些实施方案中,控制水源容器的条件,使得以高于约500标准毫升/分钟的流速将水供应至反应空间。
测量流至反应空间的水流量
可以通过若干不同方法定量水流速,包含(但不限于)测量水源容器中水的蒸气压、传递至反应器的水流速及反应室中的分压。
在一些实施方案中,通过水源容器中的水蒸气压测量水流速。可以根据水源容器中水的温度容易地测定压力。可以根据反应系统的特定特征,例如载气流量、反应空间压力、水供应管在线的任何流量或压力控制组件等,校准所得水流至反应空间的流速。
在一些实施方案中,通过测量水传递至反应器的流速定量水的流速。举例而言,可以使用流量计(flowmeter)测量流至反应器的水蒸气流量。
在一些实施方案中,可通过反应室中水分压或浓度定量水流量。
以下实施例是在先前购自ASMAmerica公司(Phoenix,Arizona)及ASMEuropeB.V.公司(Almere,Netherlands)的P3000反应器中执行。
实施例1
通过ALD法,使用交替且连续的氯化铪及水脉冲,实现0.5埃/周期的二氧化铪生长速率,其中水脉冲长度在持续时间内低于500毫秒且水源略低于室温(15℃)。此等方法条件通常在每一周期产生约15%的单层覆盖率及低羟基(-OH)表面覆盖率。
实施例2
通过在各种反应器及反应物方法条件下,将氯化铪及水交替及连续地提供至反应空间,以将二氧化铪薄膜沉积于基板上。基板温度为300℃。图2说明水脉冲时间与水源温度对沉积的二氧化铪薄膜厚度的影响。在所有温度下,将水脉冲时间自250毫秒增加至5秒均使膜生长速率增加。将水源温度自55℃增加至75℃使薄膜生长速率增加。对于指定脉冲时间,升高水源容器的温度使二氧化铪薄膜的生长速率增加。氮气用作载气。
实施例3
也在15℃、37℃、55℃、65℃及75℃的水源容器温度下,研究每一周期的二氧化铪膜的薄膜生长速率。使用水及氯化铪来沉积二氧化铪。水脉冲时间小于1秒。在各种沉积周期间隔下测量二氧化铪膜的厚度。
当水源容器源温度为15℃时,每一周期的平均生长速率为0.50埃/周期。当水源容器源温度为37℃时,每一周期的平均生长速率也为约0.50埃/周期。因此,对于15℃与37℃的水源容器源温度,生长速率大致相同。
在约55℃及更高的水源容器温度下,观察到较高生长速率。当水源容器源温度为55℃时,每一周期的平均生长速率为0.54埃/周期。当水源容器源温度为75℃时,每一周期的平均生长速率为0.55埃/周期。当水源容器源温度为65℃时,每一周期的平均生长速率也为0.55埃/周期。
通过调节水源反应器入口上节流阀(throttlevalve)的位置,使反应器压力在约4托下保持恒定。随后根据节流阀位置计算水的流速。也可使用孔(orifice)、针阀(needlevalve)或一些其它的控制来限制。流速与节流阀的打开百分比相关。接着在水脉冲期间,分析节流阀反应。随后使用相关性来计算水的流速。接着根据反应器压力、载气流速及水流速计算反应器中的水分压。
在水源容器温度为15℃下,计算出反应器中的水分压为45毫托。在水源容器温度为55℃下,计算出反应器中的水分压为约1500毫托。在水源容器温度为65℃下,计算出反应器中的水分压为约1800毫托至约2000毫托。在水源容器温度为约75℃下,计算出反应器中的水分压为约2000毫托至约2500毫托。基板温度保持在约300℃。
在水源容器温度为75℃下,达到的最高平均生长速率为0.58埃/周期。
实施例4
图3说明二氧化铪膜厚度与沉积周期数的关系。使用氯化铪及水沉积二氧化铪。水源容器温度为约75℃。每一周期的平均生长速率为约0.56埃/周期。线性关系指示在5个与40个周期之间具有一致的成核作用及膜生长。在后续沉积周期中,未观察到生长减少或抑制。
也使用卢瑟福背散射光谱(RBS)研究沉积的二氧化铪薄膜。图4说明基板表面上铪原子密度与沉积周期数的关系。
RBS数据表明,每一周期沉积约2×1014个铪原子/平方厘米,由此每一沉积周期产生大致为约21.8%的单层覆盖率。通过用每一周期的RBS表面覆盖率(2×1014个铪原子/平方厘米)除以约9.15×1014个铪原子/平方厘米的二氧化铪容积无定形密度,计算出每一周期的单层覆盖率为21.8%。比较起来,在常规水浓度脉冲下,此方法的典型单层覆盖率为约15%。因此,反应空间中水分压增加及水浓度增加将明显改良每一周期的单层覆盖率,由此以较少的沉积周期数即可形成连续膜。
也使用RBS测量沉积的二氧化铪薄膜中存在的氯量。使用含氯前体可能在沉积的薄膜中产生杂质,例如,残余氯可能并入薄膜中。意外的是,沉积的二氧化铪薄膜中存在的氯量低于RBS的0.5%的可侦测下限。利用本文所述方法制造的二氧化铪薄膜制造出氯杂质比此项技术中已知的其它方法低的膜。
图6是沉积的二氧化铪薄膜中氯含量的二次离子质谱仪(SIMS)影像。SIMS光谱显示溅射时间(在样品中的深度)与物质强度(任意单位)的关系。测量分别在55℃、65℃及75℃的源温度下使用水沉积的二氧化铪膜的氯含量。曲线显示,沉积的二氧化铪膜中的氯含量随水源温度升高而降低。也存在氢杂质(未示出)随着水源温度升高而减少的类似数据。所述资料表明,高浓度水脉冲将改良膜纯度。图6也显示二氧化铪膜在何处停止及硅基板根据以硅计数的上升趋势(up-turn)开始。
实施例5
也研究沉积的二氧化铪薄膜的电效能。图5说明隧道电压(tunnelvoltage)与沉积的二氧化铪薄膜的等效氧化层厚度(EOT)的关系。使用氯化铪及水沉积二氧化铪薄膜。水源容器源温度为75℃。对于剂量A组,水脉冲持续时间为250毫秒,而对于剂量B组,水脉冲持续时间为1000毫秒。
隧道电压与漏电流呈反比。较高隧道电压表明较低的漏电流。如图5中所示,与基于利用此项技术中已知的ALD法沉积的二氧化铪膜的预期效能相比较,在较高的反应器水分压下沉积的二氧化铪薄膜在较小EOT值下展现改良的泄漏(较高隧道电压)。泄露效能的改良可能是沉积薄膜中化学计量改良、由每一周期的单层覆盖率增加引起的膜闭合加快、较高膜密度以及沉积薄膜中杂质减少的结果。
本领域技术人员应了解,可在不偏离本发明的范围的情况下,进行各种修改及变化。类似的其它修改及变化意欲落在随附权利要求所界定的本发明的范围内。
Claims (23)
1.一种通过原子层沉积在反应空间中的基板上形成介电氧化物的方法,其中所述介电氧化物用于半导体组件,所述方法包括沉积周期,所述沉积周期包括:
向所述反应空间提供含铪及/或锆的第一反应物的气相反应物脉冲,使得其在所述基板的表面上形成不超过第一反应物单层;
自所述反应空间去除过量的所述第一反应物;
向所述反应空间提供含水的第二反应物的气相反应物脉冲,使得所述反应空间中的水分压高于500毫托,其中所述第二反应物的所述气相反应物脉冲包括比使所述基板的表面饱和需要的高至少一个数量级的水量;以及
自所述反应空间去除过量的所述第二反应物和任何反应副产物,
由此形成适合用于半导体组件的沉积的介电氧化物,其中所述沉积的介电氧化物包括所沉积的小于0.5原子百分比的氯。
2.如权利要求1所述的方法,其中重复所述沉积周期,直至获得具有所需厚度的介电氧化物。
3.如权利要求1所述的方法,其中所述第一反应物进一步包括来自由以下构成的组的元素:Ti、Al及Si。
4.如权利要求3所述的方法,其中所述第一反应物包括氯化物。
5.如权利要求4所述的方法,其中所述第一反应物包括氯化铪或氯化锆。
6.如权利要求5所述的方法,其中所述第一反应物是氯化铪且沉积二氧化铪。
7.如权利要求1所述的方法,其中所述反应空间中的水分压高于1000毫托。
8.如权利要求1所述的方法,其中所述沉积周期在每一周期中沉积大于约20%的单层。
9.如权利要求1所述的方法,其中所述基板在所述沉积周期期间的温度高于约250℃。
10.如权利要求1所述的方法,其中提供水的气相脉冲包括100毫秒或更长的脉冲长度。
11.一种通过原子层沉积在基板上形成介电氧化物的方法,所述方法包括:
交替且连续地使所述基板接触:
包括含氯及铪、氯及锆或氯以及铪及锆的前体的气相反应物,以及包括比使所述基板的表面饱和需要的高至少一个数量级的水量的气相反应物;
其中所述气相反应物被交替且重复地提供,直至获得具有所需厚度的介电氧化物,其中所述介电氧化物包括所沉积的小于0.5原子百分比的氯,并且适合用于半导体组件,
其中所述含水的气相反应物脉冲经提供使得所述反应空间中的水分压高于500毫托。
12.如权利要求11所述的方法,其中所述反应空间中的水分压高于1500毫托。
13.如权利要求12所述的方法,其中所述反应空间中的水分压高于2500毫托。
14.一种通过原子层沉积在反应空间中的基板上形成介电氧化物的方法,所述方法包括:
使基板与包括含铪及/或锆的第一前体的气相反应物脉冲以及含水的气相反应物脉冲交替及连续地接触,其中所述水经提供使得所述反应空间中的水分压高于500毫托,其中所述含水的气相反应物脉冲包括比使所述基板的表面饱和需要的高至少一个数量级的水量;及
重复所述交替及连续脉冲,直至获得具有所需厚度的介电氧化物,所述介电氧化物包括所沉积的不超过0.5原子百分比的氯,并且其中所述介电氧化物适合用于半导体组件。
15.如权利要求14所述的方法,其中所述反应空间中的水分压高于2000毫托。
16.如权利要求11所述的方法,其中所述介电氧化物包括二氧化铪或二氧化锆。
17.如权利要求14所述的方法,其中所述介电氧化物包括二氧化铪或二氧化锆。
18.如权利要求1所述的方法,其中所述沉积的介电氧化物进一步包括一种或多种来自由以下构成的组的元素:镧、铈、镨、钕、钷、钐、铒、钆、铽、镝、钬、铥、镱、镏、钡及锶。
19.如权利要求11所述的方法,其中所述介电氧化物进一步包括一种或多种来自由以下构成的组的元素:镧、铈、镨、钕、钷、钐、铒、钆、铽、镝、钬、铥、镱、镏、钡及锶。
20.如权利要求14所述的方法,其中所述介电氧化物进一步包括一种或多种来自由以下构成的组的元素:镧、铈、镨、钕、钷、钐、铒、钆、铽、镝、钬、铥、镱、镏、钡及锶。
21.如权利要求1-10或18任一项所述的方法,其中所述反应空间中的总压力是0.5托至15托。
22.如权利要求11-13、16或19任一项所述的方法,其中所述反应空间中的总压力是0.5托至15托。
23.如权利要求14、15、17或20任一项所述的方法,其中所述反应空间中的总压力是0.5托至15托。
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TWI499686B (zh) | 2015-09-11 |
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WO2011028377A3 (en) | 2011-05-26 |
KR20120059574A (ko) | 2012-06-08 |
US20110053383A1 (en) | 2011-03-03 |
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