TW202212540A - 氮化物蝕刻劑組合物及方法 - Google Patents
氮化物蝕刻劑組合物及方法 Download PDFInfo
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- TW202212540A TW202212540A TW110129961A TW110129961A TW202212540A TW 202212540 A TW202212540 A TW 202212540A TW 110129961 A TW110129961 A TW 110129961A TW 110129961 A TW110129961 A TW 110129961A TW 202212540 A TW202212540 A TW 202212540A
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- Prior art keywords
- composition
- acid
- ammonium
- microelectronic device
- titanium nitride
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- 239000000203 mixture Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 41
- 150000004767 nitrides Chemical class 0.000 title 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 45
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 22
- 239000011733 molybdenum Substances 0.000 claims abstract description 22
- 238000005530 etching Methods 0.000 claims abstract description 15
- -1 hexafluorosilicic acid Chemical compound 0.000 claims description 48
- 238000004377 microelectronic Methods 0.000 claims description 45
- 239000003112 inhibitor Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000007800 oxidant agent Substances 0.000 claims description 21
- 238000005260 corrosion Methods 0.000 claims description 19
- 230000007797 corrosion Effects 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical group OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 16
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
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- 239000008367 deionised water Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 claims description 6
- AQIIVEISJBBUCR-UHFFFAOYSA-N 4-(3-phenylpropyl)pyridine Chemical compound C=1C=NC=CC=1CCCC1=CC=CC=C1 AQIIVEISJBBUCR-UHFFFAOYSA-N 0.000 claims description 5
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical group [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 5
- 238000001312 dry etching Methods 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 3
- LXPCOISGJFXEJE-UHFFFAOYSA-N oxifentorex Chemical compound C=1C=CC=CC=1C[N+](C)([O-])C(C)CC1=CC=CC=C1 LXPCOISGJFXEJE-UHFFFAOYSA-N 0.000 claims description 3
- 238000001039 wet etching Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 4
- 229920005591 polysilicon Polymers 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
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- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 27
- 238000009472 formulation Methods 0.000 description 27
- 239000000463 material Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 17
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 10
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- 239000008139 complexing agent Substances 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 9
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- 241000894007 species Species 0.000 description 6
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- 125000006267 biphenyl group Chemical group 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
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- 239000000758 substrate Substances 0.000 description 5
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- 125000000217 alkyl group Chemical group 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
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- UKLQXHUGTKWPSR-UHFFFAOYSA-M oxyphenonium bromide Chemical compound [Br-].C=1C=CC=CC=1C(O)(C(=O)OCC[N+](C)(CC)CC)C1CCCCC1 UKLQXHUGTKWPSR-UHFFFAOYSA-M 0.000 description 1
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- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
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- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
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- 150000004760 silicates Chemical class 0.000 description 1
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- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 1
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- DGSDBJMBHCQYGN-UHFFFAOYSA-M sodium;2-ethylhexyl sulfate Chemical compound [Na+].CCCCC(CC)COS([O-])(=O)=O DGSDBJMBHCQYGN-UHFFFAOYSA-M 0.000 description 1
- WQQPDTLGLVLNOH-UHFFFAOYSA-M sodium;4-hydroxy-4-oxo-3-sulfobutanoate Chemical class [Na+].OC(=O)CC(C([O-])=O)S(O)(=O)=O WQQPDTLGLVLNOH-UHFFFAOYSA-M 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
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- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
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- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
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- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- YQIVQBMEBZGFBY-UHFFFAOYSA-M tetraheptylazanium;bromide Chemical compound [Br-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC YQIVQBMEBZGFBY-UHFFFAOYSA-M 0.000 description 1
- AHNISXOXSNAHBZ-UHFFFAOYSA-M tetrakis-decylazanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC AHNISXOXSNAHBZ-UHFFFAOYSA-M 0.000 description 1
- FDXKBUSUNHRUIZ-UHFFFAOYSA-M tetramethylazanium;chlorite Chemical compound [O-]Cl=O.C[N+](C)(C)C FDXKBUSUNHRUIZ-UHFFFAOYSA-M 0.000 description 1
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 description 1
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 description 1
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 description 1
- DAFQZPUISLXFBF-UHFFFAOYSA-N tetraoxathiolane 5,5-dioxide Chemical compound O=S1(=O)OOOO1 DAFQZPUISLXFBF-UHFFFAOYSA-N 0.000 description 1
- WBWDWFZTSDZAIG-UHFFFAOYSA-M thonzonium bromide Chemical compound [Br-].N=1C=CC=NC=1N(CC[N+](C)(C)CCCCCCCCCCCCCCCC)CC1=CC=C(OC)C=C1 WBWDWFZTSDZAIG-UHFFFAOYSA-M 0.000 description 1
- 229940051002 thonzonium bromide Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- MPSUGQWRVNRJEE-UHFFFAOYSA-N triazol-1-amine Chemical compound NN1C=CN=N1 MPSUGQWRVNRJEE-UHFFFAOYSA-N 0.000 description 1
- XDUVTZGINNGNAG-UHFFFAOYSA-M tridodecyl(methyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC XDUVTZGINNGNAG-UHFFFAOYSA-M 0.000 description 1
- GPQCSCQDQNXQSV-UHFFFAOYSA-N tridodecylazanium;chloride Chemical compound Cl.CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC GPQCSCQDQNXQSV-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 235000014393 valine Nutrition 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F4/00—Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00
-
- 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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having 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
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
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- Chemical & Material Sciences (AREA)
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Abstract
本發明提供用於選擇性地蝕刻氮化鈦之組合物及方法,其通常使所存在之鉬以及可能存在於裝置上之任何氧化鋁、二氧化矽及多晶矽不受製程影響。本發明之組合物通常能夠達成超過3.5 Å/分鐘之氮化鈦蝕刻速率,由此在圖案中提供均勻之凹部頂層及底層。
Description
本發明大體上係關於半導體製造之領域。特定言之,其係關於一種用於蝕刻微電子裝置上之氮化鈦膜的方法。
光阻遮罩常用於半導體行業中以圖案化諸如半導體或介電質之材料。在一種應用中,在雙金屬鑲嵌製程中使用光阻遮罩以在微電子裝置之後段金屬製程中形成互連件。雙金屬鑲嵌製程涉及在上覆金屬導體層(諸如銅層)的低k介電層上形成光阻遮罩。隨後根據光阻遮罩蝕刻低k介電層以形成暴露金屬導體層之通孔及/或溝槽。通常稱為雙金屬鑲嵌結構之通孔及溝槽通常使用兩個微影步驟來界定。隨後自低k介電層移除光阻遮罩,之後將導電材料沈積至通孔及/或溝槽中以形成互連件。
隨著微電子裝置之尺寸減小,達成通孔及溝槽之臨界尺寸變得愈加困難。因此,使用金屬硬式遮罩來提供對通孔及溝槽之較佳輪廓控制。金屬硬式遮罩可由鈦或氮化鈦製成,且在形成雙鑲嵌結構的通孔及/或溝槽之後藉由濕式蝕刻製程移除。濕式蝕刻製程必需使用有效地移除金屬硬式遮罩及/或光阻蝕刻殘留物,而不影響底層的金屬導體層及低k介電材料或微電子裝置上之其他材料的移除化學物質。特定言之,需要可用於濕式蝕刻製程的組合物,該等組合物選擇性地移除諸如氮化鈦之物質,同時與亦可存在於微電子裝置上之諸如鉬、AlOx、SiOx及多晶矽之金屬導電層相容。
本發明大體上提供用於在例如3D反及(NAND)快閃記憶體裝置之微電子裝置結構中產生鉬凹部之組合物及方法。在此方法中,第一步驟涉及使用高選擇率鉬蝕刻劑移除鉬層,該高選擇率鉬蝕刻劑展現出的對鉬之選擇率高於亦存在於微電子裝置上之氮化鈦。此第一步驟係已知的且可表徵為乾式或濕式蝕刻製程(參見例如IEEE Transactions on Electronic Devices, 第51卷,第12期, 2004年12月)。在第二步驟中,在本發明之一個實施例中,選擇性地蝕刻氮化鈦層,通常使存在之鉬以及可能存在於裝置上之任何氧化鋁、二氧化矽及多晶矽不受該製程影響。本發明之組合物通常能夠達成超過3.5 Å/分鐘(min)之氮化鈦蝕刻速率,由此在圖案中提供均勻之凹部頂層及底層。另外,組合物非常穩定,例如浴壽命超過24小時且存放期超過6個月。
因此,在第一態樣中,本發明提供一種組合物,其包含:
a. 水;
b. 至少一種氧化劑;
c. 至少一種含氟化物之蝕刻劑;
d. 至少一種金屬腐蝕抑制劑;
e. 至少一種pH調節劑;及視情況選用之
f. 至少一種可與水混溶之溶劑。
該等組合物適用於選擇性地蝕刻氮化鈦。組合物之選擇率視製程溫度及時間(亦即,暴露)而定。在一個實施例中,當在約50℃下量測5分鐘時,氮化鈦蝕刻相對於鉬之選擇率為約5至25。
在第一態樣中,本發明提供一種組合物,其包含:
a. 水;
b. 至少一種氧化劑;
c. 至少一種含氟化物之蝕刻劑;
d. 至少一種金屬腐蝕抑制劑;
e. 至少一種pH調節劑;及視情況選用之
f. 至少一種可與水混溶之溶劑。
如本文所用,術語「微電子裝置」對應於製造用於微電子、積體電路、能量收集或電腦晶片應用中的半導體基板、平板顯示器、相變記憶體裝置、太陽能電池板及其他產品(包括太陽能電池裝置、光伏打裝置及微機電系統(MEMS))。應瞭解,術語「微電子裝置」、「微電子基板」及「微電子裝置結構」並不意謂以任何方式為限制性的且包括最終將變成微電子裝置或微電子總成之任何基板或結構。微電子裝置可經圖案化、經毯覆、為控制件及/或為測試裝置。
如本文所用,術語「氮化鈦」及「TiN
x」對應於純氮化鈦以及包括不同化學計量及氧含量之非純氮化鈦(亦即,TiO
xN
y)。
如本文所用,「約」意欲對應於陳述值之+或-0.5%。
如本文所用,術語「低k介電材料」對應於用作分層微電子裝置中之介電材料的任何材料,其中該材料具有小於約3.5之介電常數。在某些實施例中,該等低k介電材料包括低極性材料,諸如含矽有機聚合物、含矽有機/無機混合材料、有機矽酸鹽玻璃(OSG)、TEOS、氟化矽酸鹽玻璃(FSG)、二氧化矽、氧化鋁(AlO
x)、氧化鋯(ZrO
x)及摻碳氧化物(CDO)玻璃。亦應瞭解,低k介電材料可能具有不同密度及不同孔隙率。
如本文所用,術語「金屬導體層」包含銅、鎢、鈷、鉬、鋁、釕、包含其之合金及其組合。
如本文所用,「氟化物」物種對應於包括氟離子(F
-)或共價鍵合之氟的物種。應瞭解氟化物物種可以氟化物物種包括在內或原位產生。
如下文更充分地描述,本發明之組合物可體現於廣泛多種特定調配物中。
在所有此類組合物中,其中參考重量百分比範圍(包括零下限)論述組合物之特定組分,應瞭解此類組分可存在或不存在於組合物之各種特定實施例中,且在存在此類組分之情況下,按採用此類組分之組合物的總重量計,該等組分可以低至0.0001重量%之濃度存在。
添加蝕刻劑以增加氮化鈦之蝕刻速率。所考慮之蝕刻劑包括(但不限於)氟化物源,諸如HF、氟化銨、四氟硼酸、六氟矽酸、其他含有B--F或Si--F鍵之化合物、四丁基四氟硼酸銨(TBA-BF
4)、四烷基氟化銨(NR
1R
2R
3R
4F);強鹼,諸如四烷基氫氧化銨(NR
1R
2R
3R
4OH),其中R
1、R
2、R
3、R
4可彼此相同或不同且選自氫、直鏈或分支鏈C
1-C
6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基)、C
1-C
6烷氧基(例如羥乙基、羥丙基)、經取代或未經取代之芳基(例如,苯甲基);弱鹼;及其組合。在一個實施例中,氟化物源包含HF、四氟硼酸、六氟矽酸、H
2ZrF
6、H
2TiF
6、HPF
6、氟化銨、四甲基氟化銨、四甲基氫氧化銨、六氟矽酸銨、六氟鈦酸銨,或氟化銨與四甲基氟化銨之組合。在另一實施例中,蝕刻劑包含HF、六氟矽酸或四氟硼酸。在又一實施例中,蝕刻劑為HF。
氧化劑包括在其中以蝕刻或氧化TiN
x膜中之Ti
3 +。本文中所考慮之氧化劑包括(但不限於)過氧化氫(H
2O
2)、FeCl
3、FeF
3、Fe(NO
3)
3、Sr(NO
3)
2、CoF
3、MnF
3、Oxone® (2KHSO
5·KHSO
4·K
2SO
4- CAS編號70693-62-8)、過碘酸、碘酸、氫過氧化第三丁基、氧化釩(V)、氧化釩(IV,V)、釩酸銨、多原子銨鹽(例如,過氧單硫酸銨、亞氯酸銨(NH
4ClO
2)、氯酸銨(NH
4ClO
3)、碘酸銨(NH
4IO
3)、硝酸銨(NH
4NO
3)、過硼酸銨(NH
4BO
3)、過氯酸銨(NH
4ClO
4)、過碘酸銨(NH
4IO
4)、過硫酸銨((NH
4)
2S
2O
8)、次氯酸銨(NH
4ClO))、鎢酸銨((NH
4)
10H
2(W
2O
7))、多原子鈉鹽(例如,過硫酸鈉(Na
2S
2O
8)、次氯酸鈉(NaClO)、過硼酸鈉)、多原子鉀鹽(例如,碘酸鉀(KIO
3)、過錳酸鉀(KMnO
4)、過硫酸鉀、硝酸(HNO
3)、過硫酸鉀(K
2S
2O
8)、次氯酸鉀(KClO))、多原子四甲基銨鹽(例如,四甲基亞氯酸銨((N(CH
3)
4)ClO
2)、四甲基氯酸銨((N(CH
3)
4)ClO
3)、四甲基碘酸銨((N(CH
3)
4)IO
3)、四甲基過硼酸銨((N(CH
3)
4)BO
3)、四甲基過氯酸銨((N(CH
3)
4)ClO
4)、四甲基過碘酸銨((N(CH
3)
4)IO
4)、四甲基過硫酸銨((N(CH
3)
4)S
2O
8))、多原子四丁基銨鹽(例如,四丁基過氧單硫酸銨)、過氧單硫酸、硝酸鐵(Fe(NO
3)
3)、過氧化脲((CO(NH
2)
2)H
2O
2)、過氧乙酸(CH
3(CO)OOH)、1,4-苯醌、甲苯醌、二甲基-1,4-苯醌、四氯醌(chloranil)、四氧嘧啶(alloxan)及其組合。當氧化劑為鹽時,其可為水合的或無水的。氧化劑可在製造商處,在將組合物引入裝置晶圓之前,或替代地在裝置晶圓(亦即,原位)處引入至組合物中。在一個實施例中,氧化劑包含過碘酸。
添加金屬腐蝕抑制劑以阻斷氧化劑之氧化活性。本文中所考慮之金屬腐蝕抑制劑包括(但不限於) 5-胺基-1,3,4-噻二唑-2-硫醇(ATDT)、苯并三唑(BTA)、1,2,4-三唑(TAZ)、甲苯基三唑、5-甲基-苯并三唑(MBTA)、5-苯基-苯并三唑、5-硝基-苯并三唑、苯并三唑羧酸、3-胺基-5-巰基-1,2,4-三唑、1-胺基-1,2,4-三唑、羥基苯并三唑、2-(5-胺基-戊基)-苯并三唑、1-胺基-1,2,3-三唑、1-胺基-5-甲基-1,2,3-三唑、3-胺基-1,2,4-三唑、3-巰基-1,2,4-三唑、3-異丙基-1,2,4-三唑、5-苯硫醇-苯并三唑、鹵代-苯并三唑(鹵素=F、Cl、Br或I)、萘并三唑、2-巰基苯并咪唑(MBI)、2-巰基苯并噻唑、4-甲基-2-苯基咪唑、2-巰基噻唑啉、5-胺基四唑、伸戊基四唑、5-苯基-1H-四唑、5-苯甲基-1H-四唑、丁二醯亞胺、2,4-二胺基-6-甲基-1,3,5-三𠯤、噻唑、三𠯤、甲基四唑、1,3-二甲基-2-咪唑啶酮、1,5-五亞甲基四唑、1-苯基-5-巰基四唑、二胺基甲基三𠯤、咪唑啉硫酮、4-甲基-4H-1,2,4-三唑-3-硫醇、苯并噻唑、咪唑、吲二唑(indiazole)、腺苷、咔唑、鄰磺醯苯甲醯亞胺、安息香肟及其組合。額外腐蝕抑制劑包括陽離子四級鹽,諸如苯紮氯銨、苯甲基二甲基十二烷基氯化銨、肉豆蔻基三甲基溴化銨、十二烷基三甲基溴化銨、十六烷基氯化吡錠、Aliquat 336 (Cognis)、苯甲基二甲基苯基氯化銨、Crodaquat TES (Croda公司)、Rewoquat CPEM (Witco)、十六烷基三甲基對甲苯磺酸銨、十六烷基三甲基氫氧化銨、二氯化1-甲基-1'-十四烷基-4,4'-聯吡錠、烷基三甲基溴化銨、鹽酸安普羅銨(amprolium hydrochloride)、氫氧化苄索銨(benzethonium hydroxide)、苄索氯銨、苯甲基二甲基十六烷基氯化銨、苯甲基二甲基十四烷基氯化銨、苯甲基十二烷基二甲基溴化銨、苯甲基十二烷基二甲基氯化銨、鯨蠟基氯化吡錠、膽鹼對甲苯磺酸鹽、二甲基二(十八烷基)溴化銨、十二烷基乙基二甲基溴化銨、十二烷基三甲基氯化銨(DTAC)、乙基十六烷基二甲基溴化銨、十二烷基(2-羥乙基)二甲基溴化銨、十六烷基(2-羥乙基)二甲基氯化銨、鯨蠟基三甲基對甲苯磺酸銨、十二烷基氯化吡錠(月桂基氯化吡錠)、十二烷基三甲基甲磺酸銨、十二烷基三甲基對甲苯磺酸銨、[9-(2-羧苯基)-6-二乙胺基-3-亞𠮿基]-二乙基氯化銨(若丹明B (Rhodamine B))吉拉德試劑(Girard's reagent)、十六烷基(2-羥乙基)二甲基磷酸二氫銨、十六烷基溴化吡錠、十六烷基三甲基溴化銨、十六烷基三甲基氯化銨、甲基苄索氯銨、Hyamine® 1622、Luviquat™、N,N',N'-聚氧乙烯(10)-N-牛脂-1,3-二胺基丙烷液體、奧芬溴銨(oxyphenonium bromide)、四庚基溴化銨、肆(癸基)溴化銨、通佐溴銨(thonzonium bromide)、三(十二烷基)氯化銨、三甲基十八烷基溴化銨、1-甲基-3-正辛基四氟硼酸咪唑鎓、1-癸基-3-甲基四氟硼酸咪唑鎓、1-癸基-3-甲基氯化咪唑鎓、三(十二烷基)甲基溴化銨、二甲基二硬脂基氯化銨及氯化六羥季銨。其他腐蝕抑制劑包括非離子界面活性劑(諸如PolyFox PF-159 (OMNOVA Solutions)、聚(乙二醇) (「PEG」)、聚(丙二醇) (「PPG」)、PEG-PPG共聚物(諸如Pluronic F-127 (BASF))、陰離子界面活性劑(諸如十二烷基苯磺酸、十二烷基硫酸鈉、十二烷基苯磺酸鈉)及其組合。四級鹽可充當腐蝕抑制劑(尤其對於銅及鎢)及潤濕劑兩者。較佳鎢腐蝕抑制劑包括Tomamine®醚胺,其包括(但不限於):醚四級胺(例如Q系列,諸如異癸氧基丙基雙-(2-羥乙基)甲基氯化銨、異十三烷氧基丙基雙-(2-羥乙基)甲基氯化銨、單大豆甲基氯化銨、牛脂二胺二四級銨鹽、椰油聚(15)氧乙烯甲基氯化銨)、氧化醚胺(例如AO系列,諸如雙-(2-羥乙基)異癸氧基丙基氧化胺、直鏈烷氧基丙基氧化胺、低泡烷氧基丙基氧化胺(AO-405及AO-455)),及其組合。其他氧化胺界面活性劑亦將為適用之鎢腐蝕抑制劑,包括(但不限於):十二烷基二甲基氧化胺、雙-(2-羥乙基)椰子烷基氧化胺(Aromox® C/12 W, Azko Nobel)、二甲基椰子烷基氧化胺(Aromox® DMC)、4-(苯甲氧基)吡啶N-氧化物、4-(3-苯丙基)吡啶N-氧化物,及其組合。其他適用之鎢腐蝕抑制劑包括雜環(諸如吡啶、喹啉、喹唑啉、異喹啉、吡𠯤、嘧啶、嗒𠯤、喹喏啉、啡𠯤、啡啶、2,2'-吡啶、1,4'-吡啶、4,4'-吡啶及吖啶),以及包括C
1 - 6烷基、苯基、苯甲基、苯乙基、3-苯丙基、苯甲氧基、羧基、氯基、溴基、甲氧基、硝基及氰基中之至少一者的該等雜環之衍生物,其包括(但不限於) 2-苯甲基吡啶及4-(4-硝基苯甲基)吡啶。熟習此項技術者將顯而易見地,儘管四級鹽最通常以氯化物或溴化物形式購得,但其易於用諸如硫酸根、甲磺酸根、硝酸根、氫氧根等非鹵陰離子與鹵陰離子進行離子交換。本文中亦考慮且首選該等經轉化之四級鹽。在一個實施例中,腐蝕抑制劑包括陽離子四級鹽,更佳肉豆蔻基三甲基溴化銨、苯紮氯銨、十六烷基三甲基對甲苯磺酸銨、DTAC及十六烷基三甲基氫氧化銨,其中該等氯化物在使用之前已經離子交換。
在一個實施例中,腐蝕抑制劑係選自苯甲基二甲基十二烷基氯化銨、苯甲基二甲基十四烷基氯化銨、4-(3-苯丙基)吡啶及5-甲基-苯并三唑。
本發明之組合物可包含一或多種能夠調節(亦即調整)組合物之pH的化合物(亦即pH調節劑)。組合物之pH可使用任何能夠調節組合物之pH的適合化合物來調節。pH調節劑宜為水溶性的且與組合物之其他組分相容。通常,組合物在使用點具有約-1至5、或0至4或2至4之pH。pH調節劑之非限制性實例包括無機酸及有機酸,其包括甲磺酸、乙磺酸、磷酸、硫酸、氯化氫及其類似物。
至少一種溶劑可包含水、至少一種可與水混溶之有機溶劑或其組合,其中該至少一種可與水混溶之有機溶劑係選自由式R
1R
2R
3C(OH)之化合物組成之群,其中R
1、R
2及R
3係彼此獨立的且選自由以下組成之群:氫、C
2-C
30烷基、C
2-C
30烯烴、環烷基、C
2-C
30烷氧基及其組合。舉例而言,至少一種溶劑可包含至少一種選自由以下組成之群的物種:水、甲醇、乙醇、異丙醇、丁醇及高級醇、四氫糠醇(THFA)、3-氯-1,2-丙二醇、3-氯-1-丙硫醇、1-氯-2-丙醇、2-氯-1-丙醇、3-氯-1-丙醇、3-溴-1,2-丙二醇、1-溴-2-丙醇、3-溴-1-丙醇、3-碘-1-丙醇、4-氯-1-丁醇、2-氯乙醇、二氯甲烷、三氯甲烷、乙酸、丙酸、三氟乙酸、四氫呋喃(THF)、N-甲基吡咯啶酮(NMP)、環己基吡咯啶酮、N-辛基吡咯啶酮、N-苯基吡咯啶酮、甲基二乙醇胺、甲酸甲酯、二甲基甲醯胺(DMF)、二甲亞碸(DMSO)、四亞甲基碸(環丁碸)、乙醚、苯氧基-2-丙醇(PPh)、乙基苯基酮(propriophenone)、乳酸乙酯、乙酸乙酯、苯甲酸乙酯、乙腈、丙酮、乙二醇、丙二醇(PG)、1,3-丙二醇、1,4-丙二醇、二㗁烷、丁醯基內酯、碳酸伸丁酯、碳酸伸乙酯、碳酸伸丙酯、二丙二醇、二乙二醇單甲醚、三乙二醇單甲醚、二乙二醇單乙醚、三乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單丁醚(亦即,丁基卡必醇)、三乙二醇單丁醚、乙二醇單己醚、二乙二醇單己醚、乙二醇苯醚、丙二醇甲醚、二丙二醇甲醚(DPGME)、三丙二醇甲醚(TPGME)、二丙二醇二甲醚、二丙二醇乙醚、丙二醇正丙醚、二丙二醇正丙醚(DPGPE)、三丙二醇正丙醚、丙二醇正丁醚、二丙二醇正丁醚、三丙二醇正丁醚、丙二醇苯醚、二丙二醇甲醚乙酸酯、四乙二醇二甲醚(TEGDE)、二元酯、碳酸甘油酯、N-甲醯基嗎啉、磷酸三乙酯及其組合。在一個實施例中,至少一種溶劑包含水,例如去離子水。在一個實施例中,可與水混溶之溶劑係選自乙二醇及丙二醇。
視情況地,組合物可包含至少一種錯合劑/螯合劑。然而,當氧化劑為過氧化合物(諸如過氧化氫)時,該等錯合劑為組合物之必要組分。添加錯合劑(若存在)以減少粒子產生及生長且改良組合物之存放期。所考慮之錯合劑包括(但不限於) β-二酮化合物,諸如2,4-戊二酮、乙醯基丙酮酸鹽、1,1,1-三氟-2,4-戊二酮及1,1,1,5,5,5-六氟-2,4-戊二酮;胺基酸,諸如甘胺酸、絲胺酸、脯胺酸、白胺酸、丙胺酸、天冬醯胺、天冬胺酸、麩醯胺酸、組胺酸、麩胺酸、精胺酸、半胱胺酸、纈胺酸及離胺酸;選自由以下組成之群的多質子酸及胺基多羧酸:亞胺二乙酸(IDA)、丙二酸、草酸、丁二酸、硼酸、氮基三乙酸、蘋果酸、檸檬酸、乙酸、順丁烯二酸、乙二胺四乙酸(EDTA)、乙二胺四乙酸二銨鹽(EDTA-2NH
3)、(1,2-伸環己基二氮基)四乙酸(CDTA)、二伸乙基三胺五乙酸(DTPA)、2-膦醯丁烷-1,2,4-三甲酸(PBTCA)、乙二胺二丁二酸及丙二胺四乙酸;膦酸;膦酸衍生物,諸如羥基亞乙基二膦酸(HEDP) (Dequest 2010)、1-羥基乙烷-1,1-二膦酸、氮基-參(亞甲基膦酸) (NTMP)、胺基三(亞甲基膦酸) (Dequest 2000)、二伸乙基三胺五(亞甲基膦酸) (Dequest 2060S)、乙二胺四(亞甲基膦酸) (EDTMPA);及其組合。替代地或另外,至少一種錯合劑可包括陰離子界面活性劑,其包括(但不限於)烷基硫酸鈉(諸如乙基己基硫酸鈉(NIAPROOF® 08))、烷基硫酸銨、烷基(C
10-C
18)羧酸銨鹽、磺基丁二酸鈉及其酯(例如磺基丁二酸鈉二辛酯)、烷基(C
6-C
18)磺酸鈉鹽及二陰離子磺酸鹽界面活性劑。較佳陰離子界面活性劑包括氧化二苯基二磺酸鹽,諸如購自Dow Chemical之DOWFAX系列陰離子界面活性劑,其包括DOWFAX 2A1 (氧化四丙基二苯基二磺酸鈉)、DOWFAX 3A2、DOWFAX 8390及DowFax™C6L (氧化烷二苯基二磺酸鹽),以及購自Rhone-Poulenc之RHODACAL DSB、購自Olin之POLY-TERGENT 2A1、POLY-TERGENT 2EP、購自Cytec之AEROSOL DPOS-45、購自Pilot Chemicals之CALFAX DBA-40、CALFAX 16L-35,及其類似者。氧化二苯基二磺酸鹽界面活性劑表示一類由經二磺化之氧化烷二苯基分子組成之高度陰離子表面活性劑,其中電荷由兩個磺酸根基團產生且提供極佳的乳液穩定性。替代地或另外,至少一種錯合劑可包括阻垢劑聚合物,其包括(但不限於)聚胺基醯胺(PAMAM)樹枝狀聚合物、聚(2-乙基-2-㗁唑啉)、聚乙烯亞胺(PEI)、羥化聚乙烯亞胺、經改性之聚乙烯亞胺、聚烯丙胺鹽酸鹽(PALAM)、聚(丙烯醯胺)、聚(丙烯酸)、聚(二烯丙基二甲基氯化銨)、二烯丙基二甲基氯化銨、丙烯醯胺、乙醯胍胺、聚(丙烯醯胺-共-二烯丙基二甲基氯化胺) (PAMALAM),及其組合。替代地或另外,錯合劑包括鹽,該等鹽包含銨陽離子或四烷基銨陽離子([NR
1R
2R
3R
4]
+,其中R
1、R
2、R
3及R
4可彼此相同或不同且選自由氫及C
1-C
6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基)組成之群),及選自由以下組成之群的陰離子:乙酸根、氯離子、溴離子、碘離子、硫酸根、苯甲酸根、丙酸根、檸檬酸根、甲酸根、草酸根、酒石酸根、丁二酸根、乳酸根、順丁烯二酸根、丙二酸根、反丁烯二酸根、蘋果酸根、抗壞血酸根、杏仁酸根及鄰苯二甲酸根。舉例而言,鹽可包括溴化銨及/或氯化銨。在一個實施例中,錯合劑包含氧化烷二苯基二磺酸鹽、2,4-戊二酮、絲胺酸及其任何組合中之至少一者。
在另一實施例中,本發明之組合物中之任一者可進一步包含氮化鈦及/或光阻蝕刻材料殘餘物,其中該殘餘物懸浮及/或溶解於水性組合物中。
在一個實施例中,第一態樣之組合物包含以下、由以下組成或基本上由以下組成:至少一種氧化劑、至少一種含氟化物之蝕刻劑、至少一種pH調節劑、至少一種金屬腐蝕抑制劑及視情況選用之至少一種可與水混溶之溶劑,其中組分a至f (若存在)係以以下比例存在:
a. 50至(材料之餘量)重量百分比(水);
b. 0.001至5重量百分比(氧化劑);
c. 0.001至5重量百分比(氟化物蝕刻劑);
d. 0.001至5重量百分比(金屬腐蝕抑制劑);
e. 0.1至10重量百分比(pH調節劑);及視情況選用之
f. 1至30重量百分比(可與水混溶之溶劑)。
在另一態樣中,本發明提供一種組合物,其包含:
a. 水;
b. 至少一種氧化劑,其選自過碘酸;過氧化氫、過氧化氫-脲、過硫酸銨、過氧乙酸、氫過氧化第三丁基及過錳酸鉀;
c. 至少一種蝕刻劑,其選自HF、四氟硼酸、六氟矽酸、H
2ZrF
6、H
2TiF
6、HPF
6、氟化銨、四甲基氟化銨、四甲基氫氧化銨、六氟矽酸銨及六氟鈦酸銨;
d. 至少一種金屬腐蝕抑制劑,其選自苯甲基二甲基辛基氯化銨、苯甲基二甲基十二烷基氯化銨、苯甲基二甲基十四烷基氯化銨、苯甲基二甲基十八烷基氯化銨、4-(3-苯丙基)吡啶、4-(3-苯丙基)吡啶n-氧化物、3-苯甲基吡啶N-氧化物、苯并三唑、5-甲基苯并三唑、甲苯基三唑、1,2,4-三唑,及其組合;
e. 至少一種pH調節劑,其選自甲磺酸、硫酸、鹽酸、硝酸、乙酸及磷酸;及視情況選用之
f. 至少一種可與水混溶之溶劑。
適用於蝕刻或移除氮化鈦的某些組合物利用鈍化劑,其用於減少對低k介電層之化學侵蝕且保護晶圓免受額外氧化。(參見例如以引用方式併入本文中之美國專利第10,138,117號。)在此類組合物中,有低k鈍化劑,諸如硼酸、硼酸鹽、烷氧矽烷、矽酸鈉、四甲基矽酸銨、3-羥基-2-萘甲酸、丙二酸及亞胺二乙酸。吾人已發現,本發明之組合物不需要此類鈍化劑即有效地選擇性地移除氮化鈦。因此,在另一實施例中,本發明之組合物不含低k鈍化劑。
應瞭解,在使用前製備待稀釋之組合物的濃縮形式為慣例。舉例而言,組合物可以更濃縮之形式製得,且其後在製造商處、在使用之前及/或在工廠使用期間用至少一種溶劑稀釋。稀釋比可在約0.1份稀釋劑:1份組合物濃縮物至約100份稀釋劑:1份組合物濃縮物之範圍內。應進一步瞭解,本文所描述之組合物包括隨時間推移可能不穩定的氧化劑。因此,濃縮形式可實質上不含氧化劑,且氧化劑可由製造商在使用之前及/或在工廠使用期間引入至濃縮物或經稀釋之組合物中。
藉由簡單添加各別成分且混合至均質條件,易於調配出本文所描述之組合物。此外,組合物可易於調配為在使用之時或之前混合之單封裝調配物或多部分調配物,較佳多部分調配物。多部分調配物之個別部分可在工具或在混合區/域(諸如內嵌混合機或在工具上游之儲槽中)中混合。經考慮,多部分調配物之各部分可含有當混合在一起時形成所需組合物的成分/組分之任何組合。各別成分之濃度可以組成之特定倍數廣泛變化,亦即更稀或更濃,且應瞭解,組合物可不同地且替代地包含與本文中之揭示內容一致的成分之任何組合、由與本文中之揭示內容一致的成分之任何組合組成或基本上由與本文中之揭示內容一致的成分之任何組合組成。
因此,另一態樣,本發明提供一種套組,其在一或多個容器中包含適於形成本文所描述之組合物的一或多種組分。套組之容器必須適合於儲存及運送該等移除組合物組分,例如NOWPak®容器(Advanced Technology Materials公司, Danbury, Conn., USA)。含有組合物之各組分的一或多個容器較佳地包括用於使該一或多個容器中之組分呈流體連通以供摻合及分配的構件。舉例而言,參考NOWPak®容器,氣壓可施加至該一或多個容器中之襯裡外部以使得襯裡之至少一部分內含物排出且因此實現流體連通以供摻合及分配。替代地,可向習知可加壓容器之頂部空間施加氣壓或可使用泵來實現流體連通。另外,該系統較佳地包括用於將經摻合之組合物分配至處理工具的分配口。
實質上化學惰性、無雜質、可撓性及彈性聚合膜材料(諸如高密度聚乙烯)可用於製造該一或多個容器之襯裡。處理合乎需要之襯料不需要共擠出層或障壁層,且不需要任何可能對待安置於襯裡中之組分的純度要求產生不利影響的顏料、UV抑制劑或處理劑。理想襯料之清單包括包含原生(亦即不含添加劑)聚乙烯、原生聚四氟乙烯(PTFE)、聚丙烯、聚胺基甲酸酯、聚偏二氯乙烯、聚氯乙烯、聚縮醛、聚苯乙烯、聚丙烯腈、聚丁烯等之膜。此類襯料之較佳厚度在約5密耳(0.005吋)至約30密耳(0.030吋)範圍內,例如20密耳(0.020吋)之厚度。
關於用於套組之容器,以下專利及專利申請案之揭示內容在此以各別全文引用之方式併入本文中:美國專利第7,188,644號,題為「最大限度地減少超純液體中之粒子產生的設備及方法(APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS)」;美國專利第6,698,619號,題為「可回收及可再用的襯袋桶式流體儲存及分配容器系統(RETURNABLE AND REUSABLE, BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM)」;及2008年5月9日申請之PCT/US08/63276,題為「用於材料摻合及分配之系統及方法(SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION)」,該等專利中之每一者係以引用之方式併入本文中。
在另一態樣中,本發明提供使用本文所描述之組合物自其上具有氮化鈦材料之微電子裝置的表面蝕刻氮化鈦材料之方法。舉例而言,氮化鈦材料可經移除而不實質上破壞/移除存在於微電子裝置上之金屬導體及絕緣體材料。因此,在另一實施例中,描述一種相對於鉬、鋁氧化物、二氧化矽、多晶矽,使用本文所描述之組合物自其上具有氮化鈦之微電子裝置的表面選擇性地且實質上移除氮化鈦的方法。在另一實施例中,描述一種相對於金屬導體(例如銅)、鎢及絕緣體材料,使用本文所描述之組合物自其上具有氮化鈦之微電子裝置的表面選擇性地且實質上移除氮化鈦的方法。
在蝕刻應用中,以任何適合方式將組合物塗覆至其上具有氮化鈦及/或光阻蝕刻殘留物材料之微電子裝置的表面,例如,藉由將組合物噴塗至裝置之表面上;藉由浸漬(在組合物之靜態或動態體積中)包括氮化鈦之裝置;藉由使裝置與其上吸收有組合物之另一材料(例如襯墊或纖維吸收劑施料器元件)接觸;藉由使包括氮化鈦及/或光阻蝕刻殘留物材料之裝置與循環組合物接觸;或藉由任何其他適合之手段、方式或技術,使組合物與氮化鈦膜移除接觸。塗覆可在批式或單個晶圓設備中進行,以用於動態或靜態清潔。有利地,本文中所描述之組合物係藉助於其相對於可能存在於微電子裝置結構上且暴露於組合物之其他材料(諸如金屬及絕緣材料(亦即,低k介電質)以及高k材料(諸如氧化鉿、氧化鋯、氧化鈦))對氮化鈦膜之選擇性,以高效及高度選擇性方式達成至少部分移除氮化鈦。
在使用本文中所描述之組合物自其上具有氮化鈦之微電子裝置結構移除氮化鈦時,通常在約20℃至約100℃或約30℃至約60℃範圍內之溫度下使該組合物在單晶圓工具中與裝置結構接觸持續約0.3分鐘至約30分鐘或約0.5分鐘至約3分鐘的足夠時間。此類接觸時間及溫度為說明性的,且可採用有效地自裝置結構至少部分移除氮化鈦膜之任何其他適合的時間及溫度條件。
在達成所需蝕刻/移除作用之後,該組合物可易於自其先前所塗覆之微電子裝置移除,例如藉由沖洗、洗滌或其他移除步驟,如本文所描述之組合物之給定最終用途應用中可為所需且有效的。舉例而言,裝置可用包括去離子水之沖洗溶液沖洗及/或脫水(例如,離心法脫水、N
2、蒸氣脫水等)。因此,在另一態樣中,本發明提供一種在鉬存在下在微電子裝置上選擇性地蝕刻氮化鈦之方法,其包含在約20℃至約70℃之溫度下將該微電子裝置暴露於本發明之組合物持續約30秒至約10分鐘之時段,隨後用去離子水洗滌該微電子裝置。
在另一態樣中,本發明提供根據本文所描述之方法製得之改良型微電子裝置及含有此類微電子裝置之產品。
在另一態樣中,本發明提供製造包含微電子裝置之製品的方法,該方法包含使微電子裝置與組合物接觸足夠時間而自其上具有氮化鈦之微電子裝置的表面以蝕刻方式移除氮化鈦,且將該微電子裝置併入至該製品中,其中該組合物包含以下、由以下組成或基本上由以下組成:至少一種氧化劑、至少一種蝕刻劑、至少一種腐蝕抑制劑、視情況選用之至少一種錯合劑及視情況選用之至少一種可與水混溶之溶劑。
涉及3D反及快閃記憶體結構中之閘極蝕刻的某些特定微電子裝置涉及經由如上文所描述之乾式蝕刻製程用高選擇率蝕刻劑製得鉬凹部之第一步驟。在第二步驟中,本發明之方法及組合物經實施以選擇性地蝕刻鈦。因此,在另一態樣中,本發明提供一種用於以依序步驟選擇性地蝕刻鉬及氮化鈦之方法,其包含:
a. 使用乾式蝕刻方法蝕刻鉬,隨後
b. 在鉬存在下在微電子裝置上選擇性地蝕刻氮化鈦,其包含使該微電子裝置在約20℃至約70℃之溫度下暴露於根據本發明之組合物持續約30秒至約10分鐘之時段,隨後用去離子水洗滌該微電子裝置。
在另一態樣中,本發明提供一種製品,其包含以下、由以下組成或基本上由以下組成:微電子裝置基板、該基板上之氮化鈦層及本文所描述之組合物。在一個實施例中,本發明提供一種組合物,其由上文列舉之組分a.至f.組成或基本上由其組成。
本發明可藉由其較佳實施例之以下實例進一步說明,但應瞭解,除非另外具體指示,否則包括此等實例僅出於說明之目的且不意欲限制本發明之範疇。
實例符號:
MSA:甲磺酸
12C:苯甲基二甲基十二烷基氯化銨
14C:苯甲基二甲基十四烷基氯化銨
PPP:4-(3-苯丙基)吡啶
DIW:去離子水
5m-BTA:5-甲基苯并三唑
RPM-係指用於實驗中之磁攪拌棒的每分鐘轉數。
1.氧化劑測試(過碘酸)
1)調配物及測試條件
2)蝕刻結果:
編號 | 調配物 | 製程條件 | ||||||
DIW | 過碘酸 | MSA | HF 50% | 12 C (0.2%) | 時間 | 溫度 | RPM (攪拌棒) | |
1 | 餘量 | 0 | 0.5 | 0.02 | 2 | 10 min。 | 30℃ | 360 |
2 | 餘量 | 0.02 | 0.5 | 0.02 | 2 | |||
3 | 餘量 | 0.05 | 0.5 | 0.02 | 2 | |||
4 | 餘量 | 0.1 | 0.5 | 0.02 | 2 | |||
5 | 餘量 | 0.2 | 0.5 | 0.02 | 2 |
編號 | 蝕刻速率(Å/分鐘) | TiN/Mo選擇率 | ||||
Mo | TiN | AlOx | Mo | TiN | ||
1 | 0.77 | 0.32 | 1 | 0.77 | 0.32 | 1 |
2 | 0.67 | 2.36 | 2 | 0.67 | 2.36 | 2 |
3 | 8.51 | 2.66 | 3 | 8.51 | 2.66 | 3 |
4 | 12.83 | 1.54 | 4 | 12.83 | 1.54 | 4 |
5 | 16.68 | 0.47 | 5 | 16.68 | 0.47 | 5 |
在此等實驗中,吾人注意到過碘酸濃度愈高,Mo蝕刻速率愈高。此外,過碘酸濃度愈高,TiN蝕刻速率愈低。因此,為了提高TiN/Mo選擇率,宜降低過碘酸濃度。若調配物不具有過碘酸,則TiN蝕刻速率係極低的。
2.額外氧化劑測試(過碘酸與過氧化氫比較)
1)調配物及測試條件
2)蝕刻速率結果
編號 | 調配物 | 製程條件 | |||||||
DIW | 過碘酸 | H 2O 230% | MSA | HF 50% | 12C 0.2% | 時間 | 溫度 | RPM | |
1 | 餘量 | 0.01 | 1 | 0.08 | 10 | 5 min | 45℃ | 360 | |
2 | 餘量 | 0.033 | 1 | 0.08 | 10 | ||||
3 | 餘量 | 1 | 1 | 0.08 | 10 | ||||
4 | 餘量 | 5 | 1 | 0.08 | 10 | ||||
5 | 餘量 | 10 | 1 | 0.08 | 10 |
編號 | 蝕刻速率(Å/min) | TiN/Mo選擇率 | ||||
Mo | TiN | AlOx | TEOS | 多晶Si | ||
1 | 2.98 | 34.21 | 0.82 | 1.12 | 1.36 | 11.48 |
2 | 1.41 | 6.52 | 0.70 | 1.10 | 1.24 | 4.62 |
3 | 9.20 | 10.82 | 0.77 | 1.14 | 0.19 | 1.17 |
4 | >30 | 19.83 | 0.56 | 1.21 | 0.33 | <0.66 |
5 | >30 | 24.18 | 0.53 | 1.15 | 0.50 | <0.81 |
可觀測到,當使用過氧化氫作為氧化劑時,Mo蝕刻速率因濃度而大幅度增加。
3. HF剖析測試(蝕刻劑)
1)調配物及測試條件
2)測試結果:
編號 | 調配物 | 製程條件 | ||||||
DIW | 過碘酸 | MSA | HF50% | 12C 0.2% | 時間 | 溫度 | RPM | |
1 | 餘量 | 0.02 | 0.5 | 0 | 2 | 10min | 室溫。 | 360 |
2 | 餘量 | 0.02 | 0.5 | 0.02 | 2 | |||
3 | 餘量 | 0.02 | 0.5 | 0.04 | 2 | |||
4 | 餘量 | 0.02 | 0.5 | 0.05 | 2 | |||
5 | 餘量 | 0.02 | 0.5 | 0.1 | 2 |
編號 | 蝕刻速率(Å/min) | TiN/Mo選擇率 | ||||
Mo | TiN | AlOx | TEOS | 多晶Si | ||
1 | 0.46 | 0.12 | 0.54 | 0.04 | 0.15 | 0.26 |
2 | 0.60 | 1.59 | 0.71 | 0.61 | 0.1 | 2.65 |
3 | 0.82 | 3.41 | 0.82 | 1.01 | 0.41 | 4.16 |
5 | 0.89 | 4.62 | 0.69 | 1.03 | 0.32 | 5.19 |
5 | 1.37 | 7.33 | 0.57 | 1.34 | 0.22 | 5.35 |
在此等實驗中,吾人注意到HF濃度愈高,TiN及Mo蝕刻速率愈高。在HF濃度較高的情況下,TEOS蝕刻速率亦增加,但不會達至過量程度。不含HF之調配物具有極低之TiN蝕刻速率。
4. C12濃度剖析測試(Mo抑制劑)
1)調配物及測試條件:
2)蝕刻速率結果:
編號 | 調配物 | 製程條件 | ||||||
DIW | 過碘酸 | MSA | HF 50% | 12C 0.2% | 時間 | 溫度 | RPM | |
1 | 餘量 | 0.02 | 0.5 | 0.02 | - | 10min | 室溫。 | 360 |
2 | 餘量 | 0.02 | 0.5 | 0.02 | 0.5 | |||
3 | 餘量 | 0.02 | 0.5 | 0.02 | 1 | |||
4 | 餘量 | 0.02 | 0.5 | 0.02 | 1.5 | |||
5 | 餘量 | 0.02 | 0.5 | 0.02 | 2 |
編號 | 蝕刻速率(Å/min) | TiN/Mo選擇率 | ||||
Mo | TiN | AlOx | TEOS | 多晶Si | ||
1 | >21.11 | 2.34 | 0.61 | 0.61 | 0.21 | 0.11 |
2 | 15.83 | 2.01 | 0.54 | 0.59 | 0.32 | 0.13 |
3 | 2.84 | 1.84 | 0.71 | 0.54 | 0.47 | 0.65 |
4 | 1.73 | 1.81 | 0.45 | 0.69 | 0.22 | 1.05 |
5 | 0.60 | 1.59 | 0.71 | 0.61 | 0.1 | 2.65 |
在此等實驗中,吾人注意到12C (苯甲基二甲基十二烷基氯化銨)作為Mo抑制劑係有效的。另外,12C之濃度愈高,鉬蝕刻速率愈低。12C濃度愈高,氮化鈦蝕刻速率愈低。最後,12C濃度似乎不影響諸如AlOx、TEOS及多晶Si之其他材料的蝕刻速率。
5. 額外Mo抑制劑測試(12C、14C、5m-BTA、PPP、甘胺酸)
1)調配物及測試條件
2)測試結果:
編號 | 調配物 | 製程條件 | ||||||||||
DIW | 過碘酸 | MSA (99%) | HF (49%) | 12C (0.2%) | C14 (0.2%) | PPP | 5m-BTA | 甘胺酸 | 時間 | 溫度 | RPM | |
1 | 餘量 | 0.02 | 0.5 | 0.1 | 2 | 10min | 室溫 | 360rpm | ||||
2 | 餘量 | 0.02 | 0.5 | 0.1 | 5 | |||||||
3 | 餘量 | 0.02 | 0.5 | 0.1 | 10 | |||||||
4 | 餘量 | 0.02 | 0.5 | 0.1 | 2 | |||||||
5 | 餘量 | 0.02 | 0.5 | 0.1 | 5 | |||||||
6 | 餘量 | 0.02 | 0.5 | 0.06 | 6 | 35℃ | ||||||
7 | 餘量 | 0.02 | 0.5 | 0.06 | 0.2 | |||||||
8 | 餘量 | 0.02 | 0.5 | 0.06 | 0.16 | |||||||
9 | 餘量 | 0.02 | 0.5 | 0.06 | 0.08 | |||||||
10 | 餘量 | 0.02 | 0.5 | 0.06 | 0.4 | |||||||
11 | 餘量 | 0.02 | 0.5 | 0.06 | 0.6 | |||||||
12 | 餘量 | 0.01 | 1 | 0.08 | 0.7 | 5min | 50℃ | |||||
13 | 餘量 | 0.01 | 1 | 0.08 | 1.1 | |||||||
14 | 餘量 | 0.01 | 1 | 0.08 | 1.5 | |||||||
15 | 餘量 | 0.01 | 1 | 0.08 | 0.2 | 45℃ | ||||||
16 | 餘量 | 0.01 | 1 | 0.08 | 0.7 | |||||||
17 | 餘量 | 0.01 | 1 | 0.08 | 0.2 | 0.7 |
編號 | 蝕刻速率(Å/min) | TiN/Mo選擇率 | ||||
Mo | TiN | AlOx | TEOS | 多晶Si | ||
1 | 1.37 | 7.33 | 0.57 | 1.34 | 0.22 | 5.35 |
2 | 1.01 | 3.6 | 0.81 | 1.32 | 0.19 | 3.56 |
3 | 1.16 | 4.14 | 0.76 | 1.29 | 0.45 | 3.57 |
4 | 1.72 | 1.61 | 0.64 | 1.19 | 0.61 | 0.94 |
5 | 1.72 | 1.4 | 0.6 | 1.26 | 0.16 | 0.91 |
6 | 1.88 | 16.96 | 0.78 | 0.92 | 0.34 | 9.02 |
7 | 1.77 | 15.61 | 0.56 | 0.87 | 0.57 | 8.84 |
8 | 2.28 | 17.12 | 0.81 | 0.94 | 0.43 | 7.51 |
9 | 12.33 | 15.89 | 0.62 | 1.01 | 0.57 | 1.29 |
10 | 2.26 | 16.30 | 0.66 | 0.83 | 0.22 | 7.99 |
11 | 2.26 | 1.59 | 0.78 | 0.90 | 0.38 | 6.23 |
12 | 4.50 | 62.40 | 0.82 | 1.31 | 0.55 | 13.87 |
13 | 3.90 | 61.11 | 0.67 | 1.35 | 0.71 | 15.67 |
14 | 4.10 | 62.70 | 0.51 | 1.26 | 0.34 | 15.29 |
15 | 15.76 | 37.80 | 0.77 | 1.30 | 1.22 | 2.40 |
16 | 3.50 | 37.82 | 0.88 | 1.21 | 1.03 | 10.81 |
17 | 1.78 | 34.58 | 0.58 | 1.36 | 1.11 | 19.43 |
在此等實驗中,吾人注意到12C展現出之TiN/Mo選擇率比14C (苯甲基二甲基十四烷基氯化銨)高。另外,當12C濃度增加時,Mo及TiN蝕刻速率均降低。12C、PPP (4-(3-苯丙基)吡啶)及5m-BTA (5-甲基-苯并三唑)中之每一者充當Mo抑制劑,其有助於提高TiN/Mo選擇率。最後,抑制劑組合調配物可幫助降低Mo蝕刻速率。當比較組合物15至17時,組合物17具有最低Mo蝕刻速率,其產生最高的TiN/Mo選擇率。
6. pH調節劑測試
1)調配物及測試條件
2)蝕刻速率結果:
編號 | 調配物 | 製程條件 | |||||||
DIW | 過碘酸 | MSA 99% | HF 49% | 12C 0.2% | 5m-BTA | 時間 | 溫度 | RPM | |
1 | 餘量 | 0.02 | 0.5 | 0.04 | 6 | 10min | 35℃ | 360 | |
2 | 餘量 | 0.02 | 1 | 0.04 | 6 | ||||
3 | 餘量 | 0.02 | 4 | 0.04 | 6 | ||||
4 | 餘量 | 0.005 | 1 | 0.08 | 0.7 | 3min | 50℃ | ||
5 | 餘量 | 0.005 | 0 | 0.0 | 0.7 |
編號 | 蝕刻速率(Å/min) | TiN/Mo選擇率 | ||||
Mo | TiN | AlOx | TEOS | 多晶Si | ||
1 | 1.32 | 9.23 | 0.61 | 0.68 | 0.21 | 6.99 |
2 | 0.86 | 8.48 | 0.54 | 0.61 | 0.32 | 9.86 |
3 | 1.23 | 7.62 | 0.61 | 0.70 | 0.47 | 6.20 |
4 | 13.87 | 57.80 | 0.85 | 1.33 | 0.49 | 4.17 |
5 | 4.97 | 48.83 | 1.02 | 3.01 | 0.72 | 9.82 |
觀測結果:
(1)含pH調節劑之調配物具有類似的TiN/Mo選擇率。
(2)不含pH調節劑之調配物具有較低Mo蝕刻速率,其產生較高TiN/Mo選擇率。但其缺點為顯示出較高TEOS Mo蝕刻速率。
7.溶劑測試
1)調配物及測試條件:
2)蝕刻速率結果:
編號 | 調配物 | 製程條件 | ||||||
DIW | 過碘酸 | 乙二醇 | HF 49% | 5m-BTA | 時間 | 溫度 | RPM | |
1 | 餘量 | 0.005 | 0.04 | 0.7 | 5 min | 50℃ | 360 | |
2 | 97.44 | 0.005 | 10 | 0.04 | 0.7 | |||
3 | 97.43 | 0.005 | 15 | 0.04 | 0.7 |
編號 | 蝕刻速率(Å/min) | TiN/Mo選擇率 | ||||
Mo | TiN | AlOx | TEOS | 多晶Si | ||
1 | 6.90 | 53.70 | 0.71 | 1.06 | 0.97 | 7.78 |
2 | 10.90 | 47.40 | 0.87 | 1.13 | 1.22 | 4.35 |
3 | 13.40 | 39.40 | 0.68 | 1.11 | 0.88 | 2.94 |
觀測結果:
(1)乙二醇有助於溶解調配物中之5m-BTA。
(2)但含EG之調配物具有較低TiN/Mo選擇率。
已特定參考本發明之某些實施例來詳細描述本發明,但應瞭解,可在本發明之精神及範疇內進行變化及修改。
圖1為本發明方法之流程圖。以具有包含鎢及鉬之閘極材料的裝置結構開始,使該裝置結構經歷例如乾式蝕刻(或濕式蝕刻)技術以提供閘極金屬凹部。隨後,蝕刻例如氮化鈦及/或氮化鉭之障壁金屬。用於移除氮化鈦及氮化鉭之此選擇率與現存閘極材料(諸如鎢或鉬)及高k材料(諸如AlOx或ZrOx)相容。
Claims (10)
- 一種組合物,其包含: a. 水; b. 至少一種氧化劑; c. 至少一種含氟化物之蝕刻劑; d. 至少一種金屬腐蝕抑制劑; e. 至少一種pH調節劑;及視情況選用之 f. 至少一種可與水混溶之溶劑。
- 如請求項1之組合物,其中pH為約-1至5。
- 如請求項1之組合物,其中pH為約0至4。
- 如請求項1之組合物,其中該含氟化物之蝕刻劑係選自HF、四氟硼酸、六氟矽酸、H 2ZrF 6、H 2TiF 6、HPF 6、氟化銨、四甲基氟化銨、四甲基氫氧化銨、六氟矽酸銨、六氟鈦酸銨或其組合。
- 如請求項1之組合物,其中該含氟化物之蝕刻劑為HF。
- 如請求項5之組合物,其中該金屬腐蝕抑制劑係選自十二烷基三甲基氯化銨、4-(3-苯丙基)吡啶、苯甲基二甲基十四烷基氯化銨及5-甲基苯并三唑。
- 如請求項1之組合物,其中該組合物包含選自乙二醇及丙二醇之可與水混溶之溶劑。
- 如請求項1之組合物,其中該氧化劑為過碘酸,該蝕刻劑為HF,且其中該金屬腐蝕抑制劑係選自十二烷基三甲基氯化銨、4-(3-苯丙基)吡啶、苯甲基二甲基十四烷基氯化銨及5-甲基苯并三唑。
- 一種用於在鉬存在下在微電子裝置上選擇性地蝕刻氮化鈦之方法,其包含使該微電子裝置在約20℃至約70℃之溫度下暴露於如請求項1至8中任一項之組合物持續約30秒至約10分鐘之時段,隨後用去離子水洗滌該微電子裝置。
- 一種用於在微電子裝置上以依序步驟選擇性地蝕刻鉬及氮化鈦之方法,其包含: a. 使用乾式或濕式蝕刻方法蝕刻鉬,隨後 b. 在鉬存在下在微電子裝置上選擇性地蝕刻氮化鈦,其包含使該微電子裝置在約20℃至約70℃之溫度下暴露於如請求項1至8中任一項之組合物持續約30秒至約10分鐘之時段,隨後用去離子水洗滌該微電子裝置。
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