JP6006328B2 - 金属膜の酸化 - Google Patents
金属膜の酸化 Download PDFInfo
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- JP6006328B2 JP6006328B2 JP2014541491A JP2014541491A JP6006328B2 JP 6006328 B2 JP6006328 B2 JP 6006328B2 JP 2014541491 A JP2014541491 A JP 2014541491A JP 2014541491 A JP2014541491 A JP 2014541491A JP 6006328 B2 JP6006328 B2 JP 6006328B2
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- hafnium
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- 229910052751 metal Inorganic materials 0.000 title description 137
- 239000002184 metal Substances 0.000 title description 137
- 230000003647 oxidation Effects 0.000 title description 4
- 238000007254 oxidation reaction Methods 0.000 title description 4
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000000758 substrate Substances 0.000 claims description 39
- 229910052710 silicon Inorganic materials 0.000 claims description 31
- 239000010703 silicon Substances 0.000 claims description 31
- 230000007547 defect Effects 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 239000003990 capacitor Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 6
- 230000005669 field effect Effects 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 59
- 229910052914 metal silicate Inorganic materials 0.000 description 39
- 229910044991 metal oxide Inorganic materials 0.000 description 37
- 150000004706 metal oxides Chemical class 0.000 description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 28
- 239000007800 oxidant agent Substances 0.000 description 24
- 150000004767 nitrides Chemical class 0.000 description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 14
- 235000012239 silicon dioxide Nutrition 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229910052758 niobium Inorganic materials 0.000 description 8
- 239000010955 niobium Substances 0.000 description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 241000252506 Characiformes Species 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 4
- 229910052688 Gadolinium Inorganic materials 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052769 Ytterbium Inorganic materials 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 229910052790 beryllium Inorganic materials 0.000 description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- GBAOZECSOKXKEL-UHFFFAOYSA-N copper yttrium Chemical compound [Cu].[Y] GBAOZECSOKXKEL-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052762 osmium Inorganic materials 0.000 description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 4
- 229910052702 rhenium Inorganic materials 0.000 description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 229910052706 scandium Inorganic materials 0.000 description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 description 2
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KXNLCSXBJCPWGL-UHFFFAOYSA-N [Ga].[As].[In] Chemical compound [Ga].[As].[In] KXNLCSXBJCPWGL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- FTWRSWRBSVXQPI-UHFFFAOYSA-N alumanylidynearsane;gallanylidynearsane Chemical compound [As]#[Al].[As]#[Ga] FTWRSWRBSVXQPI-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000154 gallium phosphate Inorganic materials 0.000 description 2
- LWFNJDOYCSNXDO-UHFFFAOYSA-K gallium;phosphate Chemical compound [Ga+3].[O-]P([O-])([O-])=O LWFNJDOYCSNXDO-UHFFFAOYSA-K 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
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002294 plasma sputter deposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- H01L21/02112—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/10—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances metallic oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors
-
- 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
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
- H01L21/02244—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of a metallic layer
-
- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
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- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Formation Of Insulating Films (AREA)
- Insulated Gate Type Field-Effect Transistor (AREA)
- Inorganic Insulating Materials (AREA)
- Electrodes Of Semiconductors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Description
ここで、kは、誘電体の誘電率であり(相対誘電率εrとも呼ばれることがある)、ε0は、約8.854×10−12F・m−1に等しい電気的定数であり、Aは、2枚の平板の重なりの面積であり、tは、誘電体の厚さである。より小さいコンポーネントを製造するために面積を縮小する場合、所定の静電容量を維持するために厚さも減少させることができるが、ゲート誘電体が薄すぎる場合、それが許容できない量の漏えい電圧をもたらす可能性がある。二酸化ケイ素は、約3.9のk値を有する。高k材料が二酸化ケイ素にとって代わる場合、物理的により厚い誘電体膜および潜在的により低い漏えいで、面積当たり同じ静電容量を達成することができる可能性がある。
4W×cmの抵抗率を有するn型Si(100)ウェーハを通常の(RCA)技術により清浄にした。これに続いて、ウェーハを緩衝HF(1容積/容積%)溶液で3分間エッチングした。1.23W/cm2の電力密度を用いてハフニウム金属の薄層をシリコンウェーハ上にスパッタリングした。アルゴンをスパッタリングガスとして用いた。堆積時の圧力を12mTorr一定に維持した。堆積後、試料を脱イオン水で70℃で4時間酸化した。試料を窒素で乾燥した。ESM300Jエリプソメータ(A.Woollan Co.、Inc.)を用いて、厚さ(t=4.8nm)および屈折率(n≒2)を測定した。
実施例1の二酸化ハフニウムでコーティングしたn型Si(100)ウェーハを1×10−6Torrの真空中におき、アルミニウム金属ゲートを熱蒸発によりウェーハ上に堆積させた。コンデンサ領域をパターニングした後、試料をフォーミングガス(水素5%、窒素95%)中で425℃で30分間アニールした。
高周波静電容量−電圧(HFCV)測定を、HP4284A Precision LCR(Agilent Technologies、Santa Clara CA)を用いて実施例2のコンデンサにおいて実施した。図2に示すように、示したHFCV曲線は、1×10−4cm2コンデンサについて30mVのピーク間ACシグナルを用いて100kHzで測定したが、この場合、ゲート電圧は、0.27V/秒の速度で反転から蓄積まで、および蓄積で10秒の保持時間で反転に戻すという掃引を行った。測定は、1回繰り返した。新しいデバイスの掃引で37mVである測定ヒステリシスは、第2の掃引で大幅に低下する。これは、界面に近いトラップの充てんによって説明することができる。小さいヒステリシスシフトは、おそらく誘電体における可動性電荷が低いレベルにあるという結果である。図3に1×10−4cm2〜2.5×10−3cm2のサイズの異なるコンデンサの静電容量を示す。最大の静電容量値は、すべての面積についてほぼ等しい。わずかな差は、わずかなリトグラフの変動に起因する。これらの結果は、作製した膜が卓越した均一性を有することを示すものである。
ストレスおよび電流−電圧測定は、Keithley 237 High Voltage Source Measure Unit(Keithley Instruments、Cleveland、Ohio)を用いて実施例2のコンデンサについて実施した。図4に30mVのピーク間ACテストシグナルを用いて1、10および100kHzで測定したC−V曲線を示す。少量の周波数分散を高周波数で観測することができるにすぎない。1kHzでは、遅い状態は、おそらく低周波数における界面に近いトラップの反応に起因している。ゲート漏えい電流挙動対ゲート電圧を図5に示す。1Vでは、この漏えい電流密度は、4×10−8A/cm2であり、これは、1Vにおいて同じ酸化膜換算膜厚(EOT=3.4nm)の二酸化ケイ素と比較したとき比較的低い。実際、同じ二酸化ケイ素厚の漏えい電流は、Vg=1Vで約10−8A/cm2である。フラットバンド電圧シフトの測定は、HFCV法を用いて2V振幅のストレスパルス間で行う。ストレス手順は、一定の電圧を印加することからなり、各測定の後に持続時間を増加させる。図6に1×10−4cm2コンデンサの応答を示す。グラフに2時間を超える累積ストレス時間の後に最大シフトが30mVにほぼ等しいことが示されている。この小さいシフトは、ゲートスタックに存在する低レベルの電荷についての興味深い兆候を示している。この低レベルは、1011cm−2に近似され、二酸化ハフニウム膜についてこれまでに報告された最低値の1つである。
Claims (12)
- 二酸化ハフニウム膜を製造する方法であって、
ハフニウム金属膜を脱イオン水と50℃〜100℃の温度で30分〜240分の時間にわたり接触させることによりハフニウム金属膜を酸化して、二酸化ハフニウム膜を得ることを含む、方法。 - 二酸化ハフニウム膜を製造する方法であって、
ハフニウム金属膜を脱イオン水と50℃〜100℃の温度で30分〜240分の時間にわたり接触させることにより前記ハフニウム金属膜を酸化して、前記二酸化ハフニウム膜を得ることを含み、
前記二酸化ハフニウム膜が1012cm−2未満の欠陥密度を有する、方法。 - 前記二酸化ハフニウム膜を不活性ガスにより乾燥することをさらに含む、請求項2に記載の方法。
- 前記二酸化ハフニウム膜が3.9より大きい比誘電率を有する、請求項2に記載の方法。
- 前記二酸化ハフニウム膜が界面層により基板から分離されている、請求項2に記載の方法。
- 前記二酸化ハフニウム膜が1011cm−2未満の欠陥密度を有する、請求項2に記載の方法。
- 電子的要素を製造する方法であって、
ハフニウム金属膜を基板上に堆積させること、
前記ハフニウム金属膜を脱イオン水と50℃〜100℃の温度で30分〜240分の時間にわたり接触させることにより前記ハフニウム金属膜を酸化して、二酸化ハフニウムの誘電体層を得ることであって、前記誘電体層が1012cm−2未満の欠陥密度を有すること、
前記誘電体層を不活性ガスにより乾燥すること、および
前記誘電体層を導電材料でコーティングすることを含む、方法。 - 前記誘電体層が3.9より大きい比誘電率を有する、請求項7に記載の方法。
- 基板が半導体である、請求項7に記載の方法。
- 電子的要素がコンデンサまたは電界効果トランジスタを含む、請求項7に記載の方法。
- 前記誘電体層が界面層により基板から分離されている、請求項7に記載の方法。
- 前記基板がn型シリコンを含む、請求項7に記載の方法。
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