TW201013784A - Method of fabricating semiconductor device - Google Patents
Method of fabricating semiconductor device Download PDFInfo
- Publication number
- TW201013784A TW201013784A TW098131886A TW98131886A TW201013784A TW 201013784 A TW201013784 A TW 201013784A TW 098131886 A TW098131886 A TW 098131886A TW 98131886 A TW98131886 A TW 98131886A TW 201013784 A TW201013784 A TW 201013784A
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- Prior art keywords
- layer
- substrate
- semiconductor device
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 249
- 239000000758 substrate Substances 0.000 claims abstract description 126
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims description 213
- 239000000463 material Substances 0.000 claims description 122
- 239000007789 gas Substances 0.000 claims description 65
- 238000011282 treatment Methods 0.000 claims description 34
- 238000000231 atomic layer deposition Methods 0.000 claims description 30
- 229910052732 germanium Inorganic materials 0.000 claims description 19
- -1 Si〇N Inorganic materials 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229910052734 helium Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims 3
- 230000003796 beauty Effects 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 210000002784 stomach Anatomy 0.000 claims 1
- 239000010410 layer Substances 0.000 description 275
- 150000003254 radicals Chemical class 0.000 description 69
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 40
- 239000002243 precursor Substances 0.000 description 21
- 229910001868 water Inorganic materials 0.000 description 21
- 238000000151 deposition Methods 0.000 description 16
- 230000008021 deposition Effects 0.000 description 15
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 13
- 125000000524 functional group Chemical group 0.000 description 12
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000012682 cationic precursor Substances 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 229910052735 hafnium Inorganic materials 0.000 description 7
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 7
- 239000000956 alloy Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000010432 diamond Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 238000011066 ex-situ storage Methods 0.000 description 6
- 229910000449 hafnium oxide Inorganic materials 0.000 description 6
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 229910020286 SiOxNy Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000012683 anionic precursor Substances 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910004205 SiNX Inorganic materials 0.000 description 3
- PSNPEOOEWZZFPJ-UHFFFAOYSA-N alumane;yttrium Chemical compound [AlH3].[Y] PSNPEOOEWZZFPJ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010893 electron trap Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical group [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- JXSUUUWRUITOQZ-UHFFFAOYSA-N oxygen(2-);yttrium(3+);zirconium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Y+3].[Y+3].[Zr+4].[Zr+4] JXSUUUWRUITOQZ-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- 229910017109 AlON Inorganic materials 0.000 description 1
- KUVIULQEHSCUHY-XYWKZLDCSA-N Beclometasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(Cl)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)COC(=O)CC)(OC(=O)CC)[C@@]1(C)C[C@@H]2O KUVIULQEHSCUHY-XYWKZLDCSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910004129 HfSiO Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IEJUWBNFQCUJFF-UHFFFAOYSA-M N.[O-2].[OH-].O.[Ce+3] Chemical compound N.[O-2].[OH-].O.[Ce+3] IEJUWBNFQCUJFF-UHFFFAOYSA-M 0.000 description 1
- CSVGANSVVHMKNH-UHFFFAOYSA-N [Bi+]=O.[O-2].[Nb+5].[O-2].[O-2] Chemical compound [Bi+]=O.[O-2].[Nb+5].[O-2].[O-2] CSVGANSVVHMKNH-UHFFFAOYSA-N 0.000 description 1
- VYBYZVVRYQDCGQ-UHFFFAOYSA-N alumane;hafnium Chemical compound [AlH3].[Hf] VYBYZVVRYQDCGQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 206010008129 cerebral palsy Diseases 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010616 electrical installation Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- QTTMOCOWZLSYSV-QWAPEVOJSA-M equilin sodium sulfate Chemical compound [Na+].[O-]S(=O)(=O)OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4C3=CCC2=C1 QTTMOCOWZLSYSV-QWAPEVOJSA-M 0.000 description 1
- NPEOKFBCHNGLJD-UHFFFAOYSA-N ethyl(methyl)azanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C NPEOKFBCHNGLJD-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 101150008563 spir gene Proteins 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- RVRKDGLTBFWQHH-UHFFFAOYSA-N yttrium zirconium Chemical compound [Y][Zr][Y] RVRKDGLTBFWQHH-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02304—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment formation of intermediate layers, e.g. buffer layers, layers to improve adhesion, lattice match or diffusion barriers
-
- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
-
- 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
- C23C16/308—Oxynitrides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
-
- 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
-
- 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
- H01L21/02123—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 silicon
- H01L21/02126—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 silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
- H01L21/0214—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 silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC the material being a silicon oxynitride, e.g. SiON or SiON:H
-
- 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
- H01L21/02123—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 silicon
- H01L21/02164—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 silicon the material being a silicon oxide, e.g. SiO2
-
- 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
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- H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate
Description
201013784 - 六、發明說明: 【發明所屬之技術領域】 本發明係有關於一種半導體製程’特別是有關於一 種用於金屬閘極的高介電常數閘極介電層的製3^方法。 【先前技術】 , 半導體積體電路(integrated circuit,1C )工業已經歷 快速的成長。在1C材料與設計的技術進展已造就*各個1C • 世代,每一世代的電路都比前世代來得更小更複雜。然 而,這些進展卻增加1C製造及加工的複雜度’而因應這 些進展,1C製造及加工需要類似的演進。在Ic進展課題 中,功能密度(即,單位晶片面積的内連裝置數量)普 遍增加,而幾何尺寸(即,製程所能形成的最小部件(或 線))則下降。上述尺寸微縮製程因生產效率的增加及 成本的降低而有所助益。而降低尺寸比例產生相對較高 的功率消耗(power dissipation )值,其可藉由使用低功 ® 耗裝置而獲得解決,例如互補式金氧半(complementary metal-oxide-semiconductor,CMOS)裝置。 在尺寸比例微縮發展期間,使用各種不同的材料作 為CMOS裝置的閘極電極及閘極介電層。而這些裝置的 製造希望以金屬材料作為閘極電極,且以高介電常數 (high-k)材料作為閘極介電層。通常在高介電常數材料 層與石夕基底之間會形成一界面(interfacial )層,例如氧 化層,以促進高介電常數材料層的形成並改善界面處的 電特性。然而,當形成界面層時會引起一些問題,例如 0503-A34416WF spin 201013784 後續製程期間對於高介電常數材料沉積的 特性不佳及發生氧化物再成長(re_gr〇wth)二We ing 因此’有必要尋求—種新的改善方法 上形成界面層及高介電常數材料層。 土一 【發明内容】 本發明一實施例提供一種半導體裝置的製造 包括:提供—基底;以自由基對基底進行處理,而在其 上形成-界面層,其中自由基係擇自於以下群族:含水 自由基、氮/氫自由基及硫/氫自由基;以及在界面 成一高介電常數材料層。 、本發明另-實施例提供-種半導體裝置的製造方 法’包括:提供-基底;對基底進行—第_處理,以在 基底上形成-第一介電層,第一處理包括第一自由基; 對第-介電層進行-第二處理,以在基底上形成一^二 介電層,第二處理包括不同於第一自由基的第二自由 f,其中每-第-及第二自由基包括含水自由基或氮/氣 自由基;以及在第一及第二介電層上形成一高介電常數 材料層。 '本發明又另一實施例提供一種半導體裝置的製造方 法,包括:提供一基底;對基底進行至少一處理,以在 基底上形成一界面層,處理包括電漿製程及紫外線製程 的其中一個,且該處理係使用自由基,其擇自於以下^ 族:含水自由基、氮/氫自由基及硫/氫自由基;以及在界 面層上形成一高介電常數材料層。 1 〇5〇3-A3a-!l^-r\?yr,spir , 201013784 【實施方式】 可瞭解的是以下的揭露内容提供許多不同的實施例 或範例,用以實施各個實施例的不同特徵。而以下所揭 露的内容是敘述各個構件及其排列方式的特定範例,以 求簡化本發明的說明。當然,這些特定的範例並非用以 限定本發明。再者,本說明書以下的揭露内容敘述了將 一第一特徵形成於一第二特徵之上或上方,其表示包含 了所形成的上述第一特徵與上述第二特徵是直接接觸的 實施例,亦包含了尚可將額外的特徵形成於第一特徵與 第二特徵之間而使第一特徵與第二特徵並未直接接觸的 實施例。為了達到簡化及清晰的目的,不同特徵可能以 不同尺寸比例繪示。 請參照第1目,其繪示出在一半導體基底上形成一 界面層及-南介電常數材料層的示意圖。半導體基底_ • 包括一石夕基底。基底100可包括不同的掺雜型態,取決 於習知設計需求。基底100亦包括其他單質(elementary) 半導體’例如鍺及鑽石。另外,基底100可包括一化合 物半導體及/或-合金半導體。再者,基底⑽可選擇ς
地包括-蟲晶層(epi layer),其可具有應變以提高效能, 且可包括一絕緣層上覆石夕(silicon_on_insulator, S0I 結構。 —界面層102形成於基底100上。界面層1〇2可包 括氧化石夕(Si02),其以習知熱氧化成長_叫層(例 如’熱氧化物)至所需厚度而成。然而,熱氧化物的上 0--O?-A344l6TWF<spin , 201013784 表面對於後續高介電常數材料層沉積製程具有不佳的潤 · 濕特性。藉由原子層沉積(atomic layer deposition, ALD ) 製程110或所謂的原子層化學氣相沉積(atomic layer chemical vapor deposition,ALCVD)製程(以 A+B 表示 之),於界面層102上形成一高介電常數材料層104,其 由ALD製程中二個半反應組合所構成。上述半反應其中 一個包括提供一金屬前驅物(A),例如四一(乙基曱基 胺基酸)—給(Tetrakis(ethylmethylamino)hafnium)(即, Hf[NCH3C2H5]4, TEMAH),以化學吸附基底表面。另一❿ 半反應包括提供一第二前驅物(B),例如氧物質(〇 species),以化學吸附基底表面。二個半反應之間,使 用不具活性的惰性氣體’例如Ar或N2,來清除物理吸附 於基底表面的過量前驅物A及B。通常ALD製程由前驅 物A(B)脈衝、惰性氣體清潔、前驅物B (A)脈衝、惰性氣 體清潔及重複此順序步驟所組成。因此,ALD製程i i 〇 進行-連串步驟而形成高介電常數材料多層膜。—初始 (例如,第-)冋介電常數材料層1〇4係藉由ald而形β 成於界面層102的上表面。重複ALD製程ιι〇,以在後 續形成每一同"電常數材料| 1〇4直到獲得所需的厚度 為止可觀察ALD製程的初始層具有較長的酿釀期 (inCUbati,Cy士)’其原因在於界面们02上表面的潤 濕性不佳。因此’後續的高介電常數材料層形成島狀加 層狀(iSland_t〇_layer)結構(例如,粗縫成長)。因此, 南介電常數材料層1〇4邀|而场· ,、界面層102之間的界面含有缺 陷112 ’其嚴重影響裝置效鈐 夏欢I,例如造成閘極漏電流。 201013784 界面照第2圖,其繪示出在一半導體基底上形成〜 包括二石〜高介電常數材料層的示意圖。半導體基底2〇〇 t〜石夕基底。一界面層202形成於基底200上。界而 層202可勹^ 丨闽 程而形成 氧化矽(Si〇2) ’其以習知濕化學氧化製 护"制在 相較於熱氧化成長’化學氧化物的厚度易於 ,rvrT、^於1nm。再者’化學氧化物的表面含有氦气 v -UH ) ^ Ab ^ 製程提供肖把基2〇4,其對於後續高介電常數材料層沉積 的高介電i好的潤濕特性。因此,藉由ALD製程所形成 期。 吊數材料層的初始(第一)層具有較短的醞讓 藉由爲: 介雷舍如于層沉積製程210於界面層202上形成一古 形成高介^層膝⑽製程210進行一連串步驟= 料層2〇6吊數材料多層膜。舉例來說,高介電常數材 汽介電 匕括氧化給(Hf〇2 )。一初始(例如,第一) =二。常數材料層係藉由ALD而形成於界面層202的上 成每1^ALD製程21()(例如,A+B),以在後續形 止。缺=電常數材料層2〇6直到獲得所需的厚度為 β ,可觀察到化學氧化物在塊體界面層2〇2內 206 S能基212,及在其與高介電常數材料層 AMC々界面處由大氣污染源(atm〇Sphere C〇ntaminati〇n ) & c所引起的電子陷阱2i4。此將於後續製程期間引起 氧化物再成長’使界面層202的厚度不當的增加。 界4參照第3圖’其繪示出在一半導體基底上形成一 ^面層及一向介電常數材料層的示意圖。半導體基底300 匕括—矽基底。一界面層302形成於基底300上。界面 0:^-'-A344!6TWF/spin 201013784 層302可包括氧化矽(Si〇2),其以 的熱氧化製程而形成。亦即,氧化物口 =濕式處理 成長而形成,而氧化層的上表面 圖所述的熱 對於後續高介電常數材料層沉積提供良:==以 因此,在塊體界面層302内具有較少的氫好 且對於藉由ALD製程所形成的高介 (第-)層具有較短的轉期。 數材料層的初始 藉由原子層沉積製程310於界面層3〇2上 * < 介電常數材料層3G6。ALD製程310進行—連串: 形成高介電常數材料多層膜。舉 $ …6包括氧化給⑽2)。=(:電第常, 7介電常數材料層係藉由ALD而形成於界面層搬的上 二製程310(例如,A+B),以在後續形 t母:南介電常數材料層306直到獲得所需的厚度為 3〇6°ΓΓ ’走可觀察到在界面層302與高介電常數材料層 3〇6的界面處出現電子陷胖314及大氣污染源的問題,因 =在界面處引起氧化物再成長。再者,可觀察到當界面 ^ ^ ( equivalent oxide thickness, EOT) 小於7埃(A)時’熱氧化物較第2圖的化學氧化物難以 控制。因此,對於達到先進技術的閘極堆疊設計需求(例 如,E〇T小於8埃)而言會是-種挑戰。 f參照第4圖,其繪示出在—基底上形成一界面層 及一尚介電常數材料層的方法4〇〇。上述方法4〇〇為以單 處理製程在上表面形成界面層。請參照第5A至5B圖, 其繪不出根據第4圖方法4〇〇在基底上形成界面層及高 smr 201013784 ’ 介電常數材料層的剖面示意圖。上述方法400始於區塊 410。提供一基底500。請參照第5A圖,基底5〇〇可包 括一梦(Si)基底。基底500可包括不同掺雜型態(例如, N型井區或p型井區),取決於習知設計需求。基底5〇〇 亦包括其他單質半導體,例如鍺及鑽石。另外,基底500 可包括一化合物半導體及/或一合金半導體。再者,基底 5⑼可選擇性地包括一蠢晶層(epi layer) ’其可具有應 眷 變以提高效能’且可包括一絕緣層上覆矽 (silicon-on-insulator,SOI)的結構。再者,基底 500 可 包括Ge、Ga、As、In、Sb、A1、其組合或是其他適用於 半導體裝置的基底。 方法400持續進行到區塊420,在基底500上形成一 界面層502。請參照第5B圖,以電漿製程503所產生的 自由基對破基底500的氫(H)端進行處理,以形成界面 層502。自由基可包括含水自由基。含水自由基可由含〇 _ 及Η原子的電漿所產生。基底5〇〇可置入一製程反應室, 以提供電漿製程一適當環境。在本實施例中,電漿製程 503可為HsO/Ar電漿(用於產生含水自由基),以形成 氧化矽(Si02)作為界面層502。 電漿製程503在製程反應室内可具有下列的製程條 件。電漿製程503的溫度可低於或等於5〇〇°C、總壓力在 0.005至10 Torr的範圍、電漿功率(RF功率)低於或等 於200 W、Η:◦的分壓低於或等於ο」Torr (以Ar氣體 稀釋)、Ar的流量在1 〇〇〇至200 seem的範圍及處理時 間低於或等於1分鐘。氣體流量參數可用於穩定壓力及 0503-A34416TWF/spin 201013784 反應氣體/辰度。另外,可藉由控制暴露期(exp〇sure pedod)及電漿產生自由基的全部時間來控制上述處理程 序。電装可產生於主製程反應室内或是遠距產生於預備 室(pre-camber)内且將遠距電漿供至主製程反應室内。 須注意的是電漿製程503 (例如,總壓力及H2〇的 壓力)在低溫(公00。〇較易促進界面層5〇2的厚度控 制及生成較緻密及無缺陷的塊體界面層5〇2。界面層 的等效氧化層厚度(E0T)可小於或等於7埃(A)。就 其而言,可抑制熱引擴散所造成的氧化物再成長。再者, 電,製程5G3同時改變了界面層5()2的上表面,以對後 續兩介電常數材料層的沉積(ALD或CVD)提供較佳的 潤濕特性(例如,氫氧(-OH)官能基5〇4)。另外,由 Sl〇2所構成的界面層初始形成(以其他技術)的實際厚 ^小於或等於5埃(a) ’且稍Sic>2界面層/Si基底進 行上述自由基表面處理’以改善界面層的表面條件:而 形成較佳的高介電常數材料層,將於以下說明。 y、士述方法400持續進行到區塊430,在界面層5〇2上 常數_層506。請參照第5C圖,高介電常 5〇6 .. 6包括氧化銓(Hf〇2)。高介電常數材料層 藉由ALD製程510而形成於界面層502上。ALd 耘510、進行—連串步驟而形成高介電常數材料 ,如之前所述。每一膜層係藉由在界面層5〇2 ^ =供陽離子前驅物⑷(例如,Hf物質,如 少成,並接著提供陰離子前驅物(Β)( 如Dn、 物質, 2 ,以與陽離子前驅物反應而形成一層高介電常 201013784 數材料層506。重複a了 γ^ Ί Λ / 製粒510 (例如,前驅物A+前 驅物B) ’以在後續形成每一高介電常數材料層506直 到獲得所需的厚度為止。可以理解的是也可使用其他前 驅物來形成高介電常數材料層5〇6。 另外,高介電常數材料層5〇6可包括其他介電常數 材料,諸如氮氧化給(Hf〇N)、給石夕酸鹽(腦〇)、 氮氧化铪矽(HfSiON)、氧化铪鈕(HfTa〇)、氮氧化 铪鈕(HfTaON)、氧化銓鈦(Hfn〇)、氮氧化铪鈦 (HfTiON)、氧化銓鍅(HfZr〇)、氮氧化銓锆(HfZr〇N)、 氧化铪紹(HfAlO)、氮氧化铪鋁(HfAlON)、氧化铪 鑭(HfLaO)、氮氧化銓鑭(HfLa〇N)及其組合。另外, 高介電常數材料層可藉由習知金屬有機化學氣相沉積 (metal-organic chemical vapor deposition,MOCVD )或 其他適當的CVD製程而形成。須注意的是可以原位 (in-situ)方式(例如,在ALD製程反應室内)進行界 面層及高介電常數材料層的製作。換句話說,界面層502 及高介電常數材料層506的製作從基底處理至高介電常 數材料沉積都無須暴露於大氣中。因此,較少的大氣污 染源位於基底500 (通道)/界面層502的界面,以及界 面層502/高介電常數材料層506的界面。 可以理解的是上述方法400可繼續進行半導體製 程’以形成各種不同的微電子裝置,例如積體電路的電 晶體、電阻、電容等等。舉例來說,界面層502及高介 電常數材料層506可用於形成於基底500内不同的 nMOSFET及pm〇SFET裝置的閘極介電層。 0503-A34416TWF-spin n 201013784 請參照第6A至6C圖,其繪示出另一方法以在基底 上开>成界面層及南介電常數材料層的剖面示意圖。請來 照第6A圖,基底600可包括一矽(Si)基底。基底6〇〇 可包括不同摻雜型態(例如,N型井區或p型井區), 取決於習知設計需求。基底600亦包括其他單質半導體, 例如鍺及鑽石。另外,基底600可包括一化合物半導體 及/或一合金半導體。再者,基底6〇〇可選擇性地包括一 磊晶層(epilayer),其可具有應變以提高效能,且可包 括-絕緣層上覆石夕(S0I)㈣構。再者,基底_可包 括Ge、Ga、As、In、Sb、A卜其組合或是其他適用於半 導體裝置的基底。 請參照第6B圖,以電漿製程或紫外線(uv)製程 所產生的自由基對矽基底600進行處理6〇3,以形成界面 層術。上述處理6〇3可以原位的方式或非原位(exsitu) 的方式(例如,暴露於大氣中)來進行。自由基可包括 3水自由基及/或氮/氫自由基。自由基可選擇取決於所需 的界面層602型態。基底_可置入一製程反應室,以 七供電㈣程或紫外線(UV)製程_適當環境4水自 由基可由電_uv在含原子的環境所產生。舉 =來說’含水自由基可由使用—氣體所產生,例如H2〇、 由Ϊ漿$二、I Μ’或其組合。氮/氫自由基可 ^電聚或UV在含N及H原子的環境所產生。舉例來說, 虱虱自由基可由使用_氣體所產生,例如應3、邮、 、N0、N2〇、Ar、He或其組合。界面層 可^括乳切(Si〇2),其藉由電漿製程或uv¥程 〇5〇3-A^i6rv-r ,pjr 201013784 及下列的製程條件而形成。另外,界面層可包括氮化矽 (SiNx)或氮氧化矽(SiOxNy)。 在一實施例中,電漿製程可具有下列的製程條件。 電漿製程的溫度可低於或等於500°C、總壓力在0.005至 10 Torr的範圍、電漿功率(RF功率)低於或等於200 W、 H20的分壓低於或等於0.1 Torr (以Ar氣體稀釋)以產 生含水自由基、Ar的流量在1000至200 seem的範圍及 處理時間低於或等於1分鐘。氣體流量參數可用於穩定 壓力及反應氣體濃度。另外,可藉由控制暴露期及電漿 產生自由基的全部時間來控制上述處理程序。電漿可產 生於主製程反應室内或是遠距產生於預備室内且將遠距 電漿供至主製程反應室内。 在另一實施例中,UV製程在製程反應室内可具有下 列的製程條件。UV製程的溫度可低於或等於500°C、總 壓力在0.005至10 Torr的範圍、波長(UV源)小於或 等於200nm、H20的分壓低於或等於0.1 Torr (以Ar氣 體稀釋)以產生含水自由基、NH3的流量低於或等於500 seem以產生氮/氫自由基、Ar的流量在1000至200 seem 的範圍及”啟用”UV的時間低於或等於1分鐘。氣體流量 參數可用於穩定壓力及反應氣體濃度。另外,可藉由控 制暴露期及UV產生自由基的全部時間來控制上述處理 程序。 須注意的是電漿製程及UV製程兩者(例如,總壓 力及H20的壓力)在低溫(S500°C )較易促進界面層602 的厚度控制及生成較敏密及無缺陷的塊體界面層602。界 050?-A34416TWF^spin 13 201013784 面層602的等效氧化層厚声( (A )。就其而言,: 可小於或等於7埃 長。再者,電漿製程及ϋ擴散所造成的氧化物再成 繼的上表面以董Γ後續八製程兩者同時改變了界面層 或㈣)提供較= 特介:(:材料層的沉積 基刚)。另外,由Sioti 〇Η或姻χ官能 . 所構成的界面層初始形成(以 其他技術)的實際厚度小於或等於5埃U) =7/Si基底進行上述自由基表面處理,以改善 :::下的說表:條件’而形成較佳的高介電常數材料層
請參照第6C圖,高介雷夺t u ,, Q ®…丨電常數材料層606包括氧化铪 (Hf〇2)。南介電常數材料層_係藉由則 而形成於界面層602上。⑽製程61〇進行一連串步驟 :形成高介電常數材料多層膜。每一膜層係藉由在界面 = 602的上表面提供陽離子前驅物⑷(例如,班物 質,如簡AH)而形成,並接著提供陰離子前驅物⑻ (例如,〇物質,如D2〇),以與陽離子前驅物反應而 形成一層高介電常數材料層6〇6。重複ald製程61〇(例 如,前驅物A+前驅物B),以在後續形成每一高介電常 數材料層6G6直到獲得所需的厚度為止。可以理解的是 也可使用其他前驅物來形成高介電常數材料層6%。 、另外,尚介電常數材料層606可包括其他介電常數 材料,諸如氮氧化铪(HfON)、铪矽酸鹽(HfSi〇)、 氮氧化铪矽(HfSiON)、氧化铪鈕(Hffa〇)、氮氧化 銓鈕(mTaON)、氧化铪鈦(HfTio)、氮氧化姶鈦 丨(Τη'ΤςηίΓ ,, 201013784 ’ (HfTiON)、氧化铪锆(HfZrO)、氮氧化铪锆(HfZrON)、 氧化铪鋁(HfAlO)、氮氧化铪鋁(HfAlON)、氧化铪 鑭(HfLaO)、氮氧化銓鑭(HfLaON)及其組合。另外, 高介電常數材料層可藉由習知金屬有機化學氣相沉積 (MOCVD )或其他適當的C VD製程而形成。 請參照第7A至7C圖,其繪示出另一方法以在基底 上形成界面層及高介電常數材料層的剖面示意圖。請參 照第7A圖,基底700可包括一 GaAs基底。基底700可 包括不同摻雜型態(例如,N型井區或P型井區),取 決於習知設計需求。基底700亦包括其他單質半導體, 例如鍺及鑽石。另外,基底700可包括一化合物半導體 及/或一合金半導體。再者,基底700可選擇性地包括一 磊晶層(epi layer ),其可具有應變以提高效能,且可包 括一絕緣層上覆矽(SOI)的結構。再者,基底700可包 括Ge、Ga、As、In、Sb、A1、其組合或是其他適用於半 I 導體裝置的基底。 請參照第7B圖,以電漿製程或紫外線(UV)製程 所產生的自由基對GaAs基底700進行處理703,以形成 界面層702。上述處理703可以原位的方式(例如,從基 底處理至高介電常數材料沉積期間未暴露於大氣中)或 非原位(ex situ )的方式(例如,暴露於大氣中)來進行。 自由基可包括含硫/氫自由基。基底700可置入一製程反 應室,以提供電漿製程或UV製程一適當環境。硫/氫自 由基可由使用一氣體所產生,例如H2S、(NH4)2S、NH3、 Ar、He及其組合。在一些實施例中,可使用H2S/Ar氣 0503-A34416TWF/Spin 201013784 體混合物。在其他實施例中,可使用(NH4)2S /Ar氣體混 合物。在某些其他實施例中,可使用NH3/H2S/Ar氣體混 合物。在另一些其他實施例中,可使用H2S/He氣體混合 物。界面層702可包括GaSx&/或AsSx層,其藉由電漿 製程或UV製程及下列的製程條件而形成。 在一實施例中,電漿製程在製程反應室内可具有下 列的製程條件。電漿製程的溫度可低於或等於500°C、總 壓力在0.005至10 Torr的範圍、電漿功率(RF功率)低 於或等於200 W、H2S的分壓低於或等於0.1 Torr (以惰 性氣體稀釋)、NH3的流量低於或等於500 seem (以惰 性氣體稀釋)、Ar的流量在1000至200 seem的範圍及 處理時間低於或等於1分鐘。氣體流量參數可用於穩定 壓力及反應氣體濃度。另外,可藉由控制暴露期及電漿 產生自由基的全部時間來控制上述處理程序。電漿可產 生於主製程反應室内或是遠距產生於預備室内且將遠距 電漿供至主製程反應室内。再者,可以He取代Ar或混 入He,以控制自由基濃度及動量(momentum )。 在另一實施例中,UV製程在製程反應室内可具有下 列的製程條件。UV製程的溫度可低於或等於500°C、總 壓力在0.005至10 Torr的範圍、波長(UV源)小於或 等於200nm、H2S的分壓低於或等於0.1 Torr (以Ar氣 體稀釋)以產生含水自由基、NH3的流量低於或等於500 seem (以惰性氣體稀釋)、Ar的流量在1000至200 seem 的範圍及”啟用”UV的時間低於或等於1分鐘。氣體流量 參數可用於穩定壓力及反應氣體濃度。另外,可藉由控 201013784 ::露Uv產生自由基的全部時間來控 =量:可…代A—,以控制自由基 須注意的是電漿製程及UV製程兩者(例如, 3 生力)在低溫(·。。)較易促進界面層:2 的尽度控fj及生成較緻密及無缺_塊體界面層^ 面^ 702的等效氧化層厚度(Eqt)可,)、於或等於7埃 JA)。:其而言,可抑制熱引擴散所造成的氧化物再成 H’面電漿製程及uv製程兩者同時改變了界面層 7〇2的上表面1對後續高介電常數 ^ 或CVD)提供較佳㈣濕特性 基704)。 烷〔4ΗΧ)官能 請參照第7C圖,高介電常數材料層包括氧 (Hf〇2)。南介電常數材料層7〇6係 。 而形成於界面層7〇2上。ALD製程71。進行 而形成高介電常數材料多層膜。每驟 ΐ 702的上表面提供陽離子前驅物⑷(例日如 貝’如TEMAH)而形成,並接著提供阶離子前驅 (:如’〇物質’如〇2〇) ’以與陽;子前 ) :成二層:介電常數材料層7〇6。重複ald 數材料層’以在後續形成每—高介電常 Μ蚀田#直獲㈣f的厚度為止。可以理解的是 了:刖驅物來形成高介電常數材料層鳩。 材料,語如^電讀材料層鳩可包括其他介電常數 材科#如氮氧化給(Hf〇N)、給石夕酸鹽(腦〇)、 0503-A34416T\\/p/Spjn 201013784 氮氧化铪矽(HfSiON)、氧化铪钽(HfTaO)、氮氧化 铪钽(mTaON)、氧化铪鈦(HfTiO)、氮氧化铪鈦 (HfTiON)、氧化铪锆(HfZrO)、氮氧化铪锆(HfZrON)、 氧化铪鋁(HfAlO)、氮氧化姶鋁(HfAlON)、氧化铪 鑭(HfLaO)、氮氧化铪鑭(HfLaON)及其組合。另外, 高介電常數材料層可藉由習知金屬有機化學氣相沉積 (MOCVD )或其他適當的C VD製程而形成。 請參照第8圖,其繪示出在一基底上形成一界面層 及一高介電常數材料層的方法800。上述方法800為以雙 重處理製程在上表面形成界面層。請參照第9A至9D 圖,其繪示出根據第8圖方法800在基底上形成界面層 及高介電常數材料層的剖面示意圖。上述方法800始於 區塊810。提供一基底900。請參照第9A圖,基底900 可包括一矽(Si)基底。基底900可包括不同摻雜型態(例 如,N型井區或P型井區),取決於習知設計需求。基 底900亦包括其他單質半導體,例如鍺及鑽石。另外, 基底900可包括一化合物半導體及/或一合金半導體。再 者’基底900可選擇性地包括一蟲晶層(epi layer),其 可具有應變以提高效能,且可包括一絕緣層上覆矽(SOI) 的結構。再者,基底900可包括Ge、Ga、As、In、Sb、 Al、其組合或是其他適用於半導體裝置的基底。 方法800持續進行到區塊820,在基底900上形成一 第一介電層902。請參照第9B圖,以電漿製程或UV製 程所產生的自由基對矽基底900進行處理903 (第一處 理)’以形成第一介電層902。上述處理903可以原位的 sn|v 201013784 方式(例如,從基底處理至高介電常數材料沉積期間未 暴露於大氣中)或非原位(ex situ)的方式(例如,暴露 於大氣中)來進行。自由基可包括含水自由基。含水自 由基可由電漿或UV在含Ο及Η原子的環境所產生。舉 例來說,含水自由基可由使用一氣體所產生,例如Η20、 Η2Ο2、Η2、〇2、Ν2、Ar、He或其組合。基底900可置入 一製程反應室,以提供電漿製程或UV製程一適當環境。 第一介電層902可包括氧化笮(SiOx),其藉由電漿製 程或UV製程及下列的製程條件而形成。 在一實施例中,電漿製程在製程反應室内使用一混 合氣體時,例如H20/Ar,可具有下列的製程條件。電漿 製程的溫度可低於或等於500°C、總壓力在0.005至10 Torr的範圍、電漿功率(RF功率)低於或等於200 W、 H20的分壓低於或等於0.1 Torr (以惰性氣體稀釋)、Ar 的流量在1000至200 seem的範圍及處理時間低於或等於 1分鐘。 氣體流量參數可用於穩定壓力及反應氣體濃度。另 外,可藉由控制暴露期及電漿產生自由基的全部時間來 控制上述處理程序。電漿可產生於主製程反應室内或是 遠距產生於預備室内且將遠距電漿供至主製程反應室 内。再者,可以He取代Ar或混入He,以控制自由基濃 度及動量。 在另一實施例中,UV製程在製程反應室内使用一混 合氣體時,例如H20/Ar,可具有下列的製程條件。UV 製程的溫度可低於或等於500°C、總壓力在0.005至10 0503-Α34416Τ\νΡ5Γ)ίη 201013784 Τ〇ΓΓ的氣圍、波長(uv源)小於或等於200nm、H2〇的 :壓低於或等於〇1 T〇rr (以惰性氣體稀釋)、Ar的流 里在1000至2〇〇 scem的範圍及,,啟用,,υν的時間低於 專於1分鐘。 氣體流量參數可用於穩定壓力及反應氣體濃度。另 外,可藉由控制暴露期及υν產生自由基的全部時間來 控制上述處理程序。再者’可以lie取代Ar或混入He, 以控制自由基濃度及動量。須注意的是第-處理903之
後第-介電層9G2的上表面具有氳氧(_〇H)官能基9〇4。 上述方法800持續進行到區塊83〇,在第一介電層 9。02上形成第二介電層9〇6。請參照第9C圖,以電漿製 程或UV製程所產生的自由基對第-介電層902進^處 ^ 908、(第二處理),以形成第二介電層上述處理 可以原位的方式(例如,從基底處理至高介電常數 料沉積期間未暴露於大氣中)或非原位(exsitu)的方式
(=如」暴露於大氣中)來進行。自由基可包括氮/氣自 2=/氫自由基可由電漿或uv在含原子的環 。舉例來說,氮/氫自由基可由使用一氣體所產 ’例如 NH3、N2h2、N2h4、N2、h2、N〇、N2〇、七、
If合。基底_可置人—製程反應室,以提供電 雷或UV製程一適當環境。在本實施例中,第二介 其^由乳化梦(Si〇為)或氮化梦(SiNx), 、電4程或UV製程及下列的製程條件而形成。 人氣體時實^例中,電漿製程在製程反應室内使用一混 。乱體時’例如而3/Ar,可具有下列的餘條件。電裝 0^0% 16τ\ντ ·8Π|Γ 201013784 製程的溫度可低於或等於600°C、總壓力在0.005至10 Torr的範圍、電漿功率(RF功率)低於或等於3000 W、 NH3的流量低於或等於500 seem、Ar的流量在1000至 200 seem的範圍及處理時間低於或等於5分鐘。 氣體流量參數可用於穩定壓力及反應氣體濃度。另 外,可藉由控制暴露期及電漿產生自由基的全部時間來 控制上述處理程序。電漿可產生於主製程反應室内或是 遠距產生於預備室内且將遠距電漿供至主製程反應室 内。再者,可以He取代Ar或混入He,以控制自由基濃 度及動量。 在另一實施例中,UV製程在製程反應室内使用一混 合氣體時,例如NH3/Ar,可具有下列的製程條件。UV 製程的溫度可低於或等於600°C、總壓力在0.005至10 Torr的範圍、波長(UV源)小於或等於200nm、NH3的 流量低於或等於500 seem、Ar的流量在1000至200 seem 的範圍及”啟用”UV的時間低於或等於5分鐘。 氣體流量參數可用於穩定壓力及反應氣體濃度。另 外,可藉由控制暴露期及UV產生自由基的全部時間來 控制上述處理程序。再者,可以He取代Ar或混入He, 以控制自由基濃度及動量。須注意的是第二處理908之 後第二介電層906的上表面具有氨(-NHX)及/或氫氧 (-OH)官能基909。 須注意的是不同的氣體組合可用於第一及第二處理 903及908。在一實施例中,上述處理包括一氣體混合物, 例如 H20/Ar、H20/02/Ar、H202/Ar 或 H2/02/Ar,藉由調 0503-A?44i6TWF/spin 201013784 . > 整Η及Ο自由基的活性及濃度以形成sicg^。上述處理 包括一氣體混合物,例如H 〇/N /Ar、H 〇 / h2/〇高,藉由調整h、〇&n自由基(介電層 雜3%)的活性及濃度以形成sioxNyHZ。在其他實施例 中,上述處理包括一氣體混合物,例如ΝΗ3/ΑΓ、Ν2Η2/Αι·、 N2H4/Ar、N2/H2/Ar 或 NH3/H2/Ar,藉由調整 η、〇&ν 第 自由基(介電層内Ν摻雜>3%)的活性及濃度以形成 Si〇xNyHz。上述處理包括一氣體混合物,例如N〇/^/Ar、 N20/H2/Ar或NH3/NO/Ar ,藉由調整H、0&n自由基的 活性及濃度以形成Si〇xNyHz。再者,第—及第二處理9们 及908可為第一電装+第二電聚、第一 uv+第二電聚 電槳:+第一 UV及第一 uv+第二UV。 須注意的是電漿製裎及uv製程兩者(例如,總壓 力及h20的壓力)在低溫($谓。c )較易促進第一介電 層902的厚度控制(等效氧化層厚度(EOT) $7埃(A)) 及生成較緻密及無缺陷的塊體界面層。就其而言,可抑 =熱^擴散所造成的氧化物再成長。再者,電聚製程及 製程兩者同時在低溫(测。C )改變了界面層的上表 :’以對後續高介電常數材料層的沉積(ALD或CVD) =較,的潤濕特性(例如,權X或_〇h官能基_ )。 γΓ而s ’第二介電層9G6的實際厚度小於或等於3埃 ’因此第一及第二介電層9〇2及9〇 或等於7埃(A)。 一人^法800持續進行到區塊84〇,在界面層(第一及第 叫,電層902及906)上形成高介電常數材料層912。第 201013784 二處理908之後,第二介電層9〇6的上表面戽有·〇 或_NHX官能基909,以對後續高介電常數材料 及/
(ALD或CVD)提供較佳的潤濕界面。請參照第積 咼介電常數材料層912包括氧化铪(Hf〇2)。言介。〆 數材料層912係藉由ALD製程914而形成於二’層電9二 及906上。ALD製程914進行一連串步驟而形成高曰介電 常數材料多層膜,如之前所述。每一膜層係輳由在界面 層902及906的上表面提供陽離子前驅物(A)(例如,
Hf物質,如TEMAH)而形成,並接著提供陰離子前驅 物(B)(例如,〇物質,如d2〇),以與陽離子前驅物 反應而形成一層高介電常數材料層912。重複ALD製程 914 (例如,前驅物A+前驅物B) ’以在後續形成每一 南介電常數材料層912直到獲得所需的厚度為止。可以 理解的是也可使用其他前驅物來形成高介電常數材料層 912。 另外,尚介電常數材料層912可包括其他介電常數 材料’諸如氮氧化铪(HfON)、铪矽酸鹽(HfSiO)、 氮氧化铪矽(HfSiON)、氧化銓鈕(Η仃aO)、氮氧化 給组(HfTaON)、氧化铪鈦(η仃iO)、氮氧化铪鈦 (HfTiON)、氧化铪錘(HfZr0)、氮氧化銓鍅(HfZr〇N)、 氧化給銘(HfAlO)、氮氧化铪鋁(HfAlON)、氧化铪 _ (HfLaO)、氮氧化铪鑭(IifLaON)及其組合。另外, 尚介電常數材料層可藉由習知金屬有機化學氣相沉積 (MOCVD )或其他適當的CVD製程而形成。 可以理解的是上述方法400可繼續進行半導體製 0503-A344) 6TWF/spi 201013784 程’以形成各種不同的微電子裝置’例如積體電路的電 晶體、電阻、電容等等。舉例來說,界面層5〇2及高介 電常數材料層506可用於形成於基底500内不同的 nMOSFET及pMOSFET裝置的閘極介電層。 請參照第10A至10D圖,其繪示出根據第8圖方法 800的另一實施例而在基底上形成界面層及高介電常數 材料層的剖面示意圖。第10圖的實施例同樣在一基底上 進行雙重處理製程以及沉積高介電常數材料層。^此, 除了以下所述的差異之外,第10圖的半導體裝置相似於 第9圖的半導體裝置。請參照第1〇A圖,一基底1〇〇〇可 包括一矽(Si)基底。基底1000可包括不同摻雜型態(例 如’N型井區或p型井區),取決於習知設計需求。基 底1000亦包括其他單質半導體,例如鍺及鑽石。另外, 基底1000可包括一化合物半導體及/或一合金半導體。再 者,基底1000可選擇性地包括一磊晶層(epi iayer), 其可具有應變以提高效能,且可包括一絕緣層上覆石夕 (SOI)的結構。再者,基底1〇〇〇可包括Ge、Ga、As、 ΙΠ、%、A1、其組合或是其他適用於半導體裝置的基底。 ττν Γ參照帛_圖,—介電層職係藉由電漿製程或 ^程職生的自絲對⑦基底麵崎處理翻 :處理)而形成。上述處理1〇〇3可以原位的方式(例 ,基底處理至高介電常數材料沉積期間未暴露於大 來)一或==(exsiiu)的方式(例如’暴露於大氣幻 施例中,自由基可包括氮7氫自由基。氮/ 風自由基可由電在含μη 201013784 生。舉例來說,氮/氫自由基可由使用一氣體所產生,例 如 NH3、N2H2、N2H4、N2、H2、NO、N20、Ar、He 或其 組合。基底1000可置入一製程反應室,以提供電漿製程 或UV製程一適當環境。在本實施例中,第介電層1002 可藉由電漿製程或UV製程及下列的製程條件而形成。 在一實施例中,電漿製程在製程反應室内使用一混 合氣體時,例如NH3/Ar,可具有下列的製程條件。電漿 製程的溫度可低於或等於600°C、總壓力在0.005至10 Torr的範圍、電漿功率(RF功率)低於或等於3000 W、 NH3的流量低於或等於500 seem、Ar的流量在1000至 200 seem的範圍及處理時間低於或等於5分鐘。 氣體流量參數可用於穩定壓力及反應氣體濃度。另 外,可藉由控制暴露期及電漿產生自由基的全部時間來 控制上述處理程序。電漿可產生於主製程反應室内或是 遠距產生於預備室内且將遠距電漿供至主製程反應室 内。再者,可以He取代Ar或混入He,以控制自由基濃 度及動量。 在另一實施例中,UV製程在製程反應室内使用一混 合氣體時,例如NH3/Ar,可具有下列的製程條件。UV 製程的溫度可低於或等於600°C、總壓力在0.005至10 Torr的範圍、波長(UV源)小於或等於200nm、NH3的 流量低於或等於500 seem、Ar的流量在1000至200 seem 的範圍及”啟用”UV的時間低於或等於5分鐘。 氣體流量參數可用於穩定壓力及反應氣體濃度。另 外,可藉由控制暴露期及UV產生自由基的全部時間來 0503-A?4416TWF/spin 201013784 控制上述處理程序。再者’可以He取代八1*或混入1^, 以控制自由基濃度及動量。 在本實施例中,介電層1002可包括一氮化矽 (SlNx) ’其上表面具有氨(-NHJ官能基1004。在一 =實施例中,介電層10〇2可包括一氮氧化矽(SiOxNy), 其上表面具有氨(_ΝΗχ)官能基。介電層1002 —開始形 成部分的界面層。 “凊參照第1〇C圖,對分別含有SiNx& Si再氧化的介 1層1002進行處理1〇〇8,以形成介電層1〇〇6。再氧化 製程可在氧化環境下進行熱退火。在本實施例中,藉由 電裝製程或UV製程所產生的自由基對介電層1〇〇2的上 表面及其與矽基底1000的界面進行處理1008。因此,介 電層1006形成於矽基底1〇〇〇上,而一介電層1〇〇23形 成於介電層1_上。上述處理1GG8可以原位的方式(例 2,未暴露於大氣中)或非原位(ex Situ)的方式(例如, 攸基底處理至高介電常數材料沉積期間暴露於大氣中) 來進仃。在本實施例中,自由基可包括含水自由基。含 水自由基可由電漿或uv在含〇及H原子的環境所產 生。舉例來說,含水自由基可由使用一氣體所產生,例 h20、H2〇2、h2、〇2、n2、Ar、He 或其組合基底 可置入製程反應室,以提供電漿製程或uv製程 —適當環境。介電層祕可藉由下列的製程條件而形成。 人友在一實施例中’電漿製程在製程反應室内使用—混 :=體時,例如H20/Ar,可具有下列的製程條件。電裝 ’程的溫度可低於或等於50(rc、總壓力在0·005至1〇 snip 26 050^.. 201013784
Torr的範圍、電漿功率(RF功率)低於或等於200 W、 H20的分壓低於或等於0.1 Torr (以惰性氣體稀釋)、Ar 的流量在1000至200 seem的範圍及處理時間低於或等於 1分鐘。 氣體流量參數可用於穩定壓力及反應氣體濃度。另 外,可藉由控制暴露期及電漿產生自由基的全部時間來 控制上述處理程序。電漿可產生於主製程反應室内或是 遠距產生於預備室内且將遠距電漿供至主製程反應室 内。再者,可以He取代Ar或混入He,以控制自由基濃 度及動量。 在另一實施例中,UV製程在製程反應室内使用一混 合氣體時,例如H20/Ar,可具有下列的製程條件。UV 製程的溫度可低於或等於500°C、總壓力在0.005至10 Torr的範圍、波長(UV源)小於或等於200nm、H20的 分壓低於或等於0.1 Ton·(以惰性氣體稀釋)、Ar的流 量在1000至200 seem的範圍及”啟用”UV的時間低於或 等於1分鐘。 氣體流量參數可用於穩定壓力及反應氣體濃度。另 外,可藉由控制暴露期及UV產生自由基的全部時間來 控制上述處理程序。再者,可以He取代Ar或混入He, 以控制自由基濃度及動量。 在本實施例中,經過電漿或UC製程之後,介電層 1006可包括氧化矽(SiOx),而介電層1002a可包括氮 氧化矽(SiOxNy)。在其他實施例中,介電層1006可包 括氧化矽氮氧化矽(SiOxNy)。介電層1002a及1006係 050?'A?』416TV/F'spin 201013784 構成界面層。 須注意的是不同的氣體組合可用於第一及第二處理 1003及1008。在一實施例中,上述處理包括一人 物,例如 H2〇/Ar、H2〇/〇2/Ar、η2〇2/Αγ 或 H2/〇2/Ar,^ 由調整Η及Ο自由基的活性及濃度以形成Si〇#〆上述 處理包括一氣體混合物,例如H2〇/N2/Ar、H2〇y2/N2/Ar 或IVCV/N2’藉由調整H、〇&n自由基(介電層内n 摻雜S3%)的活性及濃度以形成Si〇xNyH^在其他實施 例中,上述處理包括一氣體混合物,例如NH3/Ar、 KIVAr、ΝΛ/Αγ、N^HVAr 或 NHVHVAr,藉由調整 H、 〇及N自由基(介電層内N摻雜>3%)的活性及濃度以 形成SiOxNyHz。上述處理包括一氣體混合物,例如 NO/HVAr、Ν2〇/Η2/Αγ 或丽3/N0/Ar,藉由調整 H、〇 及 N自由基的活性及濃度以形成si〇xNyHz。再者,第一及 第二處理1003及1008可為第一電漿+第二電漿、第一 uv+第二電漿、第一電漿+第二uv及第一 uv+第二uv。 須注意的是電漿製程及uv製程兩者(例如,總壓 力及Η20的壓力)在低溫(S500t )較易促進介電層1〇〇6 的厚度控制(等效氧化層厚度(Ε〇τ) 埃()及生 成較緻密及無缺陷的塊體界面層。就其而言,可抑制熱 引擴散所造成的氧化物再成長。再者,電漿製程及uv 製程兩者同時在低溫(s_t)改變了界面層的上表面, 以對後續南介電常數材料層的沉積(ALD或Cvd)提供 ,佳的=濕特性(例如,(_〇H)或(_NHJ官能基〗⑼9)。 就其而δ,介電層1〇〇2a的實際厚度小於或等於3埃 201013784 * (A),因此介電層l〇〇2a及1006總EOT小於或等於7 埃(A)。 ' 第二處理1008之後,介電層i〇02a的上表面具有 (-0H)及/或(-NHX)官能基10〇9,以對後續高介^常 數材料層的沉積(ALD或CVD)提供較佳的潤濕界面。 請參照第10D圖,高介電常數材料層1〇12包括氧化鈐 (Hf〇2)。高介電常數材料層1012係藉由ALD製程 籲而形成於界面層(介電層1002a及1006)上。ALD製程 1014進行一連串步驟而形成高介電常數材料多層膜,如 之前第9圖所述。每一膜層係藉由在界面層(介電層 1002a及1006)的上表面提供陽離子前驅物(A)(例如, Hf物質,如TEMAH)而形成,並接著提供陰離子前驅 物(B)(例如,〇物質,如〇2〇),以與陽離子前驅物 反應而形成一層高介電常數材料層1012。重複ALD製程 1014 (例如,前驅物A+前驅物B ),以在後續形成每一 _ 高介電常數材料層1012直到獲得所需的厚度為止。可以 理解的是也可使用其他前驅物來形成高介電常數材料層 1012。 另外,高介電常數材料層1012可包括其他介電常數 材料,諸如氮氧化铪(Hf〇N)、給石夕酸鹽(HfSiO)、 氮氧化铪矽(HfSiON)、氧化铪钽(HfTaO)、氮氧化 铪钽(HfTaON)、氧化铪鈦(HfTiO)、氮氧化铪鈦 (HfTiON)、氧化铪锆(HfZrO)、氮氧化铪鍅(HfZrON)、 氧化铪鋁(HfAlO)、氮氧化铪鋁(HfAlON)、氧化铪 鑭(HfLaO)、氮氧化铪鑭(HfLaON)及其組合。另外, 050?-A344i6TWF/spin 29 201013784 高介電常數材料層可藉由習知金屬有機化學氣相沉積 (MOCVD)或其他適當的CVD製程而形成。 可以理解的是上述基底9〇〇及1〇〇〇可繼續進行半 導體製程,以形成各種不同的微電子裝置,例如積體電 路的電晶體、電阻、電容等等。舉例來說,界面層(介 電層902及906及介電層3002a及1〇〇6)及高介電常數 材料層912及1012可用於不同的nFET& pFET裝置的 閘極介電層。舉例來說,可在高介電常數材料層上形成 一金屬層。金屬層包括N功函數(w〇rk functi〇n)金屬 (N-金屬)或P功函數(p_金屬)。金屬層可藉由各種 沉積技術而形成,例如物理氣相沉積vap〇r deposition,PVD )或濺鍍、CVD、ALD、電鍍或其他適當 的技術。-多晶♦ (pGly)層可藉由㈣或其他適當的 技術而形成於金屬層上。—枝科(hani邮⑻層可 行成於多晶石夕層上。上述各個層可圖案化而形成習知閘 本發明不同實施例具有不同的優點。舉例來說,以 上敘述的方法在低溫下提供一緻密且表面改變的界面 層。因此…些優點包括:⑴基底(通道)/界面層界 面鈍化,(2)因高介電常數前驅物而改變界面層表面(較 接的潤濕界面);⑶在高介電常數材料沉積之後,界 面層/高介電常數材料的界面鈍化;⑷界面處的 染源少;⑸抑制熱引擴散;⑷閘極介電層的e〇t 因此,閘極介電層的Ε〇τ符合先盡的技術 要求(例如,45·以下)。因此,上述方法相容於現行 f6T\V^ λΟ 201013784 而 CMOS製程技術,而可輕易整合至現行 置技術。可㈣解的是Μ實施例提供不^設備及裝 對於所有實施:而言,没有特定的優點是二= 有通常知識者能狗清楚理解以下的二:屬技術領域中具 中具有通常知冑Μ技術領域 基礎以® “ 解具丌利用本發明揭示内容為 =〜核更動其㈣程及結構而完成 同於上述實施例的優點。所屬: w:〜㈣节知識者亦能夠理解不脫離本發明之精 ;2圍的等效構造可在不脫離本發明之精神和範圍内 作任意之更動、替代與潤飾。舉例來說,上述實施例的 =面層及高介電常數材料層可用於前閘極(gatefirst)製 程後閘極(gate last)製程以及包括前閘極製程及後閘 極製程的混合製程,以形成具有高介電常數閘極介電層 及金屬閘極配置的裝置。
0-、03'Α34416T'VF/sDin 201013784 【圖式簡單說明】 第1圖係繪示屮 電常數材料層的、、、半導體基底上形成界面層及高介 墙、撕、万法示意圖。 第2圖係繪示屮 電常數材料岸、半導體基底上形成界面層及高介 第3圖;I方在?意圖。 電常數材料層的其、半導體基底上形成界面層及高介 ^ 4 θ 一方法示意圖。 基底上形發明各個實施例之在半導體 第5Α至5γ /呵"電常數材料層的方法流程圖。 層及^介電常數康圖方法來形成界面 介電常二-方法來形成界面層及高 第7Α至7C圖係綠示出 士、十^ 高介電常數材料層的剖面示出意又圈另Γ方法來形成界面層及 某底y,係緣不出根據本發明各個實施例之在半導體 基底上形成界面層及在牛V體 圖。 罨吊數材科層的另一方法流程 第9A至9D圖係緣示出根據第 層及高介電常數材料層的剖面示意圖。“成界面 第】0A至j〇d圖係緣示 以雙重處理製程形成界面層,且在半導體^實施例之 介電常數材料層。 在.V體基底上沉積高 f主要元件符號說明j Μ丁WF.snir 201013784 ' 100、'200、300、500、600、700、900、1000〜基底; 102、202、302、502、602、702〜界面層; 104、206、306、506、606、706、912、1012〜高介 電常數材料層; 110、210、310、510、610、710、914、1014〜原子 層沉積(ALD)〜製程; 112〜缺陷; 204、504、904〜氳氧(-OH)官能基; ® 212〜過量氫氧官能基; 214、312〜電子陷阱; 304〜上表面; 400、800〜方法; 410、420、430、810、820、830、840〜區塊; 503〜電漿製程; 603 ' 703、903、908、1003、1008〜處理; Λ 604、909〜官能基; 9 704〜烷(-SHX)官能基; 902〜第一介電層; 906〜第二介電層; 1002、1002a、1006〜介電層; 1004〜氨(-NHX)官能基; 1009〜(-OH)及/或(-NHX)官能基; AMC〜大氣污染源。 〇5〇3-A3^4i6TWF^snin
Claims (1)
- 201013784 七、申請專利範圍: 包括: 1. 一種半導體裝置的製造方法 提供一基底; =由基對祕底進行處理,而在其上形成一界面 :白::5亥自由基係擇自於以下群族:含水自由基、氮/ 虱自由基及硫/氫自由基;以及 在該界面層上形成一高介電常數材料層。 方本2.^申#專利粑圍第1項所述之半導體裝置的製造 中形成該界面層包括藉由-電漿製程或-紫外 線製程產生該自由基。 如申明專利範圍第2項所述之半導體裝置的製造 :法,其中該電衆製程條件包括溫度低於戰、總壓力 •005 s lOTorr的範圍、電漿功率低於2〇〇 w及 低於1分鐘。 4.如中睛專利㈣帛2項所述之半導體裝置的製造 八中务'外線製程條件包括溫度低於500t:、總壓力 0.005至lOTorr的範圍、波長低於2〇〇nm及時間低於 1分鐘。 .如申明專利乾圍第1項所述之半導體裝置的製造 :法’其中該自由基由一氣體所產生,其擇自於以下群 h2〇、H2〇2、H2、〇2、N2、h2S、(顺4)2S、腿3、Ν2ΐί2、 出4、No、沁〇、Ar、He及其組合。 、6.如申請專利範圍第5項所述之半導體裝置的製造 方法,其中該含水自由基由一 Η2〇/Αγ混合氣體所產生, 且Η2〇的分壓低於0.1 Ton·。 201013784 7·如申請專利範圍第5項所述之半導體裝置的製造 方法,其中該氮/氫自由基由一 NH3/Ar混合氣體所產生, 且NH3的流量低於5Q0 sccm。 8.如申请專利範圍第5項所述之半導體裝置的製造 方法,其中該硫/氫自由基由一 Hj/He混合氣體所產生, 且h2s的分壓低於0丨Torr。 、9.如申請專利範圍第1項所述之半導體裝置的製造 方法二其中藉由原子層沉積或金屬有機化學氣相沉積形 成該高介電常數材料層。 、10.如申請專利範圍第丨項所述之半導體裝置的製造 方法’其中藉由原位方式形成該界面層及該高 材料層。 11.如巾料利範圍第〗項所述之半導體裝置的製造 其中該基底包括:Si、Ge、Ga、As、In,Al 的其中一個。 12^ 4專鄉圍帛i項所述之半導體裝置的製造 中該界面層包括:Si〇2、Si〇N、Ge〇2、Ge〇N、 a x NSx、A1SX 及 AsSx 的其中一個。 13.種半導體裝置的製造方法,包括: 提供一基底; -介=基行一第一處理’以在該基底上形成-電層,該第一處理包括第一自由美. 成4該層進行一第二處二在該基广… 的第-自由基,其中每一第一及第二自由基包括含水自 0503-A?d416TWF/SDin 35 201013784 由基及氮/氫自由基的其中一個;以及 在該第一及第二介電層上形成一高介電常數材料 層。 14. 如申請專利範圍第13項所述之半導體裝置的製 造方法,其中該第一及該第二自由基的其中一個由一氣 體所產生,其擇自於以下群族:NH3、N2H2、N2H4、N2、 NO、N20、H20、H202、H2、02、Ar、He 及其組合。 15. 如申請專利範圍第13項所述之半導體裝置的製 造方法,其中每一第一及第二處理包括電漿製程及紫外 線製程的其中一個。 16. 如申請專利範圍第15項所述之半導體裝置的製 造方法,其中該電漿製程條件包括以下其中一個: 使用一 H20/Ar混合氣體,且H20的分壓低於0.1 Torr、Ar的流量在1000至200 seem的範圍、溫度低於 500°C、總壓力在0.005至10 Torr的範圍、電漿功率低於 200 W及時間低於1分鐘;以及 使用一 NH3/Ar混合氣體,且NH3的流量低於500 seem、Ar的流量在1000至200 seem的範圍、溫度低於 600°C、總壓力在0.005至10 Torr的範圍、電漿功率低於 3 kW及時間低於5分鐘。 17. 如申請專利範圍第15項所述之半導體裝置的製 造方法,其中該紫外線製程條件包括以下其中一個: 使用一 H20/Ar混合氣體,且H20的分壓低於0.1 Torr、Ar的流量在1000至200 seem的範圍、温度低於 500°C、總壓力在0.005至10 Torr的範圍、波長低於200nm 〇5(n-A^4-il6TWF snin 201013784 及時間低於1分鐘;以及 使用一 NIVAr混合氣體,且NH3的流量低於5〇〇 seem、Ar的流量在1〇〇〇至200 seem的範圍、溫度低於 6〇〇°C、總壓力在0.005至丨〇 Torr的範圍、波長低於2〇〇nm 及時間低於5分鐘。 18.—種半導體裝置的製造方法,包括: 提供一基底;對該基底進行至少一處理,以在該基底上形成一界 面層,該處理包括電漿製程及紫外線製程的其中一個, 且該處理係使用自由基,其擇自於以下群族:含水自由 基、氮/氫自由基及硫/氫自由基;以及 在該界面層上形成一高介電常數材料層。 ^ 19.如申請專利範圍第18項所述之半導體裝置的製 造方法,其中形成該界面層包括: 對該基底進行-第—處理,以在該基底上形成一第 介電層,該第一處理包括第一自由基; 對該第—介電層進行—第二處理,以在該基底上形 第"電層,該第二處理包括不同於該第一自由美 的第二自由基。 土 20·如中請專利範㈣18項所述之半導體裝置的製 &方法,其中形成該界面層包括: 在矽基底上形成一 Si〇2層及一 Si0N層的其 個;以及 胃/、τ ,該SiO』/石夕基底及該Si〇N層/石夕基底的其中 進仃至少一處理; 〇5(Γ、-Α34416TWF/Spin 37 201013784 其中該Si02層及該SiON層的其中一個的初始實際 厚度不超過5埃。
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CN101685777A (zh) | 2010-03-31 |
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