KR20160091615A - Etching composition for a titanium layer - Google Patents
Etching composition for a titanium layer Download PDFInfo
- Publication number
- KR20160091615A KR20160091615A KR1020150011935A KR20150011935A KR20160091615A KR 20160091615 A KR20160091615 A KR 20160091615A KR 1020150011935 A KR1020150011935 A KR 1020150011935A KR 20150011935 A KR20150011935 A KR 20150011935A KR 20160091615 A KR20160091615 A KR 20160091615A
- Authority
- KR
- South Korea
- Prior art keywords
- titanium
- titanium film
- etching
- film
- sulfonic acid
- Prior art date
Links
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000010936 titanium Substances 0.000 title claims abstract description 73
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 73
- 238000005530 etching Methods 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 22
- 125000005210 alkyl ammonium group Chemical group 0.000 claims abstract description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 8
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 4
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 2
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- IKJFYINYNJYDTA-UHFFFAOYSA-N dibenzothiophene sulfone Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3C2=C1 IKJFYINYNJYDTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000004065 semiconductor Substances 0.000 abstract description 14
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000012528 membrane Substances 0.000 abstract description 6
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- -1 nitrate salt compound Chemical class 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 6
- 229910021341 titanium silicide Inorganic materials 0.000 description 6
- 238000001312 dry etching Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- 238000001039 wet etching Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 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 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- BRDOFYPYQFDHOQ-UHFFFAOYSA-N butyl acetate;hexanoic acid Chemical compound CCCCCC(O)=O.CCCCOC(C)=O BRDOFYPYQFDHOQ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000003405 preventing effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000005382 boronyl group Chemical group 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- QGAKFUJUPKPDCN-UHFFFAOYSA-M tetraoctylazanium;fluoride Chemical compound [F-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QGAKFUJUPKPDCN-UHFFFAOYSA-M 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
- C23F1/30—Acidic compositions for etching other metallic material
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
Description
본 발명은 향상된 티타늄막 식각속도 및 하부막에 대한 보호 효과를 확보할 수 있는 티타늄막 식각액 조성물에 관한 것이다.The present invention relates to a titanium film etchant composition capable of securing an improved titanium film etching rate and a protective effect on a lower film.
최근 IT 기술의 발달은 휴대폰, 디지털 카메라, MP3, USB 메모리와 같은 휴대기기의 고성능화, 소형화를 가속화시키고 있다. 더욱이 현재 대두되고 있는 스마트폰은 손안의 PC를 지향하며 발전을 거듭하고 있다. 이러한 제품들은 기존의 PC(personal computer)와 동등한 능력을 지녀야하며, 이를 구현하기 위해서는 초고속, 대용량, 저소비 전력, 우수한 성능 및 신뢰성을 가진 반도체에 대한 기술 개발이 요구되고 있다.Recently, the development of IT technology is accelerating the high performance and miniaturization of portable devices such as mobile phones, digital cameras, MP3 and USB memories. Moreover, the smart phone that is emerging now is developing with the aim of PC in hand. These products must have the capability equivalent to that of a conventional personal computer (PC). To realize this, it is required to develop a technology for a semiconductor having a high speed, large capacity, low power consumption, excellent performance and reliability.
일반적으로 반도체 장치는 하나의 트랜지스터와 하나의 커패시터(Capacitor)를 단위셀로 하여 제조되고 이러한 반도체 장치의 트랜지스터는 일반적으로 MOS 구조이다.Generally, a semiconductor device is manufactured by using one transistor and one capacitor as a unit cell, and the transistor of such a semiconductor device is generally a MOS structure.
이러한 MOS 구조의 트랜지스터는 소스(Source) 전극, 게이트(Gate) 전극 및 드레인(Drain) 전극 구조로 이루어지며 실리콘 기판 위에 소스(Source) 전극, 드레인(Drain) 전극 단자를 만들고 이 단자에 전류를 흘려 준다. 게이트(Gate) 전극 단자에는 전압을 걸 수 있도록 되어 있는데 맨 상층부는 금속으로 주로 Al 이 쓰이고 이 금속층 밑에 산화막은 보통 실리콘 산화물이 사용된다. 이때 전극들 간에 원할한 전류의 흐름을 위해 일반적으로 티타늄실리사이드(TiSi)막을 배선으로 이용하여 전술한 소스 전극, 게이트 전극 및 드레인 전극을 연결시킨다. The MOS transistor has a source electrode, a gate electrode, and a drain electrode structure. A source electrode and a drain electrode terminal are formed on a silicon substrate, a current is supplied to the terminal, give. The gate electrode terminal is made to be able to apply a voltage, and the uppermost layer is made of metal mainly made of Al, and the oxide layer is usually made of silicon oxide under the metal layer. At this time, the source electrode, the gate electrode, and the drain electrode are connected to each other by using a titanium silicide (TiSi) film as a wiring in order to smoothly flow current between the electrodes.
이러한 티타늄실리사이드막 형성 방법은 소스 전극, 게이트 전극 및 드레인 전극이 형성된 기판 상에 티타늄막을 형성시키고 형성된 티타늄막을 어닐(anneal)시킨 후, 이를 이용하여 티타늄실리사이드막을 성막한다. 이때 어닐 처리를 수행하는 동안 기판이 대기 중에 노출되어 티타늄막이 산소 또는 수증기와 반응함으로써 산화티타늄막이 만들어진다. 산화티타늄막은 강한 결합력으로 인해 티타늄실리사이드막 형성에 문제가 되며 이로 인해 쇼트 현상을 일으킨다. 또한, 반도체 공정이 더욱 복잡해지고 미세화됨에 따라 이러한 불량에 따른 신뢰성 저하의 문제가 심각해지고 있다. The titanium silicide film forming method includes forming a titanium film on a substrate on which a source electrode, a gate electrode, and a drain electrode are formed, annealing the formed titanium film, and forming a titanium silicide film using the annealed titanium film. During the annealing process, the substrate is exposed to the atmosphere, and the titanium film reacts with oxygen or water vapor to form a titanium oxide film. The titanium oxide film is problematic in the formation of the titanium silicide film due to its strong bonding force, which causes a short-circuit phenomenon. Further, as the semiconductor process becomes more complicated and finer, the problem of lowering the reliability due to such defects becomes serious.
따라서, 티타늄실리사이드막의 불량을 방지하기 위해 실리사이드 공정 이후에 티타늄막을 식각하는 공정은 필수적이다. 통상적으로 플라즈마 등을 이용한 건식 식각 또는 식각액을 이용하는 습식 식각이 사용된다. 습식 식각은 건식 식각에 비하여 장비의 구성이 간단하고 공정 시 시간이 단축된다는 장점이 있다. 또한, 습식 식각 공정에 사용되는 식각액의 수요는 반도체가 응용되는 산업의 발전과 함께 급속도로 성장하였다. Therefore, a process of etching the titanium film after the silicide process is essential to prevent defects of the titanium silicide film. Dry etching using plasma or wet etching using an etching solution is usually used. Wet etching has a merit that the construction of the equipment is simple and the time for the process is shorter than that of the dry etching. In addition, the demand for etchant used in the wet etching process has grown rapidly with the development of the industries to which the semiconductor is applied.
반도체 공정의 경우 건식 식각 공정이 많이 사용되고 있다. 건식 식각 공정은 할로겐 식각 가스를 이용하고 있으며, 습식 식각에 비해 이방성 프로파일을 가지며 식각 제어력이 우수하다는 장점이 있다. 그러나 건식 식각을 위해선 고가의 장비가 필요하고 대면적화에 어려움이 있으며 식각속도가 느리기 때문에 생산성면에서 불리하다는 단점이 있다. 이에 티타늄의 경우 건식 식각 보다는 습식 식각에 대한 연구가 활발히 진행되고 있다.In the semiconductor process, dry etching process is widely used. The dry etch process utilizes a halogen etch gas, has an anisotropic profile compared to wet etch, and has an advantage of excellent etch control. However, dry etching requires expensive equipment, difficulty in large-scale fabrication, and a disadvantage in terms of productivity because the etching speed is slow. In the case of titanium, wet etching has been actively studied rather than dry etching.
그 예로서, 대한민국 특허공개 제2000-0028870호는 불산, 과요오드산 및 황산으로 이루어진 에칭제 조성물을 제시하고 있다. For example, Korean Patent Publication No. 2000-0028870 discloses an etchant composition comprising hydrofluoric acid, periodic acid, and sulfuric acid.
대한민국 특허공개 제2011-0019604호는 과산화수소, 함불소 화합물, 아미노기와 카르복실기를 동시에 함유하는 화합물, 질산염 화합물, 고리형 아민 화합물 및 물로 구성된 식각액 조성물을 제안하고 있다.Korean Patent Publication No. 2011-0019604 proposes an etching solution composition comprising hydrogen peroxide, a fluorine compound, a compound containing both an amino group and a carboxyl group, a nitrate salt compound, a cyclic amine compound and water.
이들 특허들은 불소를 이용하여 티타늄막의 효율적인 식각을 꾀하고 있으나, 그 효과가 충분하지 않을 뿐 아니라 티타늄 이외의 금속을 동시에 제거하거나 용매로 물을 사용하여 다른 막질에 대한 손상을 발생시켜 품질과 생산성이 저하되는 문제가 발생한다.These patents have attempted to efficiently etch titanium films using fluorine, but their effects are not sufficient. In addition, metals other than titanium are simultaneously removed, or water is used as a solvent to cause damage to other films, The problem of degradation occurs.
이에 티타늄막을 빠른 속도로 식각함과 동시에 함께 적층되는 다른 층들에 대한 보호 효과를 확보하기 위해 다각적으로 연구한 결과, 본 출원인은 유기 술폰산, 알킬암모늄 플루오라이드 및 유기 용매를 사용할 경우, 티타늄 식각 반응에 있어서 상기 문제점을 해결할 수 있음을 확인하여 본 발명을 완성하였다.As a result of various investigations in order to secure a protective effect on the other layers stacked together at the same time as the titanium film is etched at a high rate, the Applicant has found that when the organic sulfonic acid, the alkylammonium fluoride and the organic solvent are used, And thus the present invention has been completed.
따라서, 본 발명의 목적은 티타늄막 식각에 있어서 우수한 식각특성 및 다른 막질에 대한 부식 방지 효과를 갖는 티타늄막 식각액 조성물을 제공하는 것이다.Accordingly, an object of the present invention is to provide a titanium film etchant composition having an excellent etching property in titanium film etching and a corrosion preventing effect on other film quality.
상기 목적을 달성하기 위해, 본 발명은 유기 술폰산, 알킬암모늄 플루오라이드 및 유기 용매를 포함하는 티타늄막 식각액 조성물을 제공한다.In order to achieve the above object, the present invention provides a titanium film etchant composition comprising an organic sulfonic acid, an alkylammonium fluoride, and an organic solvent.
상기 티타늄막 식각액 조성물은 비수계인 것을 특징으로 한다.The titanium film etchant composition is characterized by being non-aqueous.
상기 유기 술폰산은 하기 화학식 1로 표시되는 것을 특징으로 한다.The organic sulfonic acid is represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
(상기 화학식 1에서, R1은 명세서 내 설명한 바와 같다)(Wherein R 1 is as described in the specification)
상기 알킬암모늄 플루오라이드는 하기 화학식 2로 표시되는 것을 특징으로 한다.Wherein the alkylammonium fluoride is represented by the following general formula (2).
[화학식 2](2)
(상기 화학식 2에서, R2 내지 R5 및 X는 명세서 내 설명한 바와 같다)(Wherein R 2 to R 5 and X are as described in the specification)
상기 티타늄막 식각액 조성물은 전체 조성물 100 중량%를 만족하도록, 유기 술폰산 0.1 내지 20 중량%, 알킬암모늄 플루오라이드 0.1 내지 20 중량%, 및 잔부로 유기 용매를 포함하는 것을 특징으로 한다.The titanium film etchant composition comprises 0.1 to 20% by weight of an organic sulfonic acid, 0.1 to 20% by weight of an alkyl ammonium fluoride, and an organic solvent in an amount sufficient to satisfy 100% by weight of the total composition.
본 발명에 따른 티타늄막 식각액 조성물은 티타늄막 식각속도가 우수하며 물을 포함하지 않아 실리콘 산화막, 게이트 소재막, 알루미늄막에 대한 부식이 억제되므로 반도체 제조공정에 있어 향상된 식각 특성으로 생산성 및 신뢰성을 크게 향상시킬 수 있다. The titanium film etchant composition according to the present invention has an excellent etch rate of titanium film and does not contain water, thereby suppressing corrosion of silicon oxide film, gate material film and aluminum film. Therefore, productivity and reliability can be improved Can be improved.
본 발명은 반도체 제조 공정에서 티타늄막의 습식 식각시 다른 막질에 대한 손상없이 티타늄막만을 효과적으로 식각하는 티타늄막 식각액 조성물을 제시한다.The present invention discloses a titanium film etchant composition that effectively etches only a titanium film without damaging other films during wet etching of the titanium film in a semiconductor manufacturing process.
티타늄의 식각에 있어서 티타늄막의 특수한 화학적 성질로 인하여 불소 이온을 필요로 하며 이에 따라 일반적으로 불산을 많이 사용한다. 그러나 불산은 물과 반응하게 되면, 부식성이 매우 강해지며 이로 인해 하부막을 공격하거나 장비를 손상시키는 등의 부작용을 보이게 된다. Due to the special chemical properties of the titanium film in the etching of titanium, fluorine ions are required, and accordingly, fluorocarbons are generally used. However, when Fosan reacts with water, the corrosion becomes very strong, which causes side effects such as attacking the lower membrane or damaging the equipment.
이에 본 발명에서는 유기 술폰산, 알킬암모늄 플루오라이드 및 유기 용매로 이루어진 비수계 식각액 조성물을 이용하여 티타늄막 식각 공정이 보다 안정적이고 효과적으로 진행될 수 있도록 한다. Accordingly, in the present invention, the titanium film etching process can be performed more stably and effectively by using the non-aqueous etching solution composition composed of the organic sulfonic acid, the alkylammonium fluoride, and the organic solvent.
자세히 설명하면, 알킬암모늄 플루오라이드는 분자 구조 내 함유된 불소 이온이 해리되어 티타늄막의 표면 식각 반응에 참여한다. 또한, 유기 술폰산은 상기 알킬암모늄 플루오라이드와 반응하여 불산(HF)과 바이플루오라이드 이온(HF2 -)을 생성하며 이는 식각액의 수소이온농도(pH)를 낮춘다. 이에 따라 생성된 HF와 HF2 -의 반응성이 높아져 티타늄막의 식각속도를 향상시킨다. 이에 더해서, 상기 유기 술폰산의 술폰산기는 티타늄막과 함께 적층되는 다른 막, 일례로 실리콘 산화막과 알루미늄막 표면에 피막을 형성하여 부식 방지 효과를 향상시킨다. Specifically, the alkylammonium fluoride dissociates the fluorine ions contained in the molecular structure and participates in the surface etch reaction of the titanium film. In addition, the organic sulfonic acid reacts with the alkylammonium fluoride to produce hydrofluoric acid (HF) and bifluoride ion (HF 2 - ), which lowers the pH of the etching solution. As a result, the reactivity between HF and HF 2 - produced increases, thereby improving the etching rate of the titanium film. In addition, the sulfonic acid group of the organic sulfonic acid improves the corrosion preventing effect by forming a film on another layer laminated with the titanium film, for example, a silicon oxide film and an aluminum film surface.
특히, 유기 술폰산과 알킬암모늄 플루오라이드가 반응을 통해 형성되는 산물은 물이 존재하는 경우 활성이 급격히 높아져 티타늄막 이외의 막질을 공격하여 부식이 일어난다. 그러나 본 발명에서는 유기 용매를 사용하기 때문에 이러한 문제를 원천적으로 차단할 수 있을 뿐 아니라 식각 공정 중 불소 이온에 의해 식각된 티타늄을 용해시켜 식각이 보다 효과적으로 진행될 수 있는 잇점을 확보한다. Particularly, when the organic sulfonic acid and the alkylammonium fluoride are formed through the reaction, the product is rapidly activated when water is present, attacking the membranes other than the titanium membrane and causing corrosion. However, since the organic solvent is used in the present invention, it is possible to prevent such a problem from occurring, and it is possible to dissolve the titanium etched by the fluorine ions in the etching process to secure an advantage that the etching can proceed more effectively.
이하 각 조성을 설명한다.Each composition will be described below.
본 발명에서의 유기 술폰산은 술폰산기(-SO3H)를 가지는 유기산의 한 종류로서 하기 화학식 1로 표시되는 것을 특징으로 한다.The organic sulfonic acid in the present invention is a kind of an organic acid having a sulfonic acid group (-SO 3 H) and is characterized by being represented by the following formula (1).
(상기 화학식 1에서,(In the formula 1,
R1은 C1 내지 C25의 알킬기, C3 내지 C25의 사이클로알킬기 또는 C6 내지 C20의 아릴기이고, 이때 아릴기는 분자 내 적어도 하나의 탄소 원자가 C1 내지 C12의 알킬기, C3 내지 C12의 사이클로알킬기기로 치환 또는 비치환된다)R 1 is C 1 to C 25 alkyl, C 3 to C 25 in the cycle of the alkyl group or a C 6 to C 20 aryl group, wherein the aryl group molecule at least one carbon atom C 1 to alkyl groups of C 12, C 3 To C 12 cycloalkyl group)
본 발명에서 언급하는 “알킬기”는 직쇄형 또는 분지형을 포함하고, 메틸, 에틸, n-프로필, i-프로필, n-부틸, 이소부틸, 펜틸, 헥실, 이소헥실, 헵틸, 4,4-디메틸펜틸, 옥틸, 2,2,4-트리메틸펜틸, 노닐 등을 포함한다.The term " alkyl group " used in the present invention includes straight or branched alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n- butyl, isobutyl, pentyl, hexyl, Dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, and the like.
본 발명에서 언급하는 “사이클로알킬기”는 탄소 원자의 완전히 포화된 및 부분적으로 불포화된 탄화수소 고리로, 사이클로프로필, 사이클로프로필메틸, 사이클로펜틸, 사이클로헥실, 아다만틸, 및 치환 및 비치환 보르닐, 노르보르닐 및 노르보르네닐을 포함한다.As used herein, a "cycloalkyl group" is a fully saturated and partially unsaturated hydrocarbon ring of carbon atoms, including cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, adamantyl, and substituted and unsubstituted boronyl, Norbornyl, and norbornenyl.
본 발명에서 언급하는 “아릴기”는 모노사이클릭 또는 비사이클릭 방향족 고리로 6개 이상의 원자를 갖는 1개 이상의 고리를 함유하며, 22개 이하의 원자를 함유하는 5개 이하의 고리가 존재할 수 있고, 인접 탄소 원자 또는 적합한 헤테로원자 사이에 이중 결합이 교대로 존재할 수 있다. 구체적으로 페닐, 바이페닐, 터페닐, 스틸벤, 나프틸, 안트라세닐, 페난트릴, 파이레닐 등을 포함한다.The "aryl group" referred to in the present invention includes one or more rings having 6 or more atoms in a monocyclic or bicyclic aromatic ring and up to 5 rings containing up to 22 atoms may be present And there can be alternating double bonds between adjacent carbon atoms or suitable heteroatoms. Specific examples include phenyl, biphenyl, terphenyl, stilbene, naphthyl, anthracenyl, phenanthryl, pyrenyl and the like.
본 발명에서 언급하는 “비치환”이란 수소 이외의 치환기를 갖지 않는 것을 의미한다.The term " unsubstituted " in the present invention means having no substituent other than hydrogen.
바람직하기로 상기 R1은 C1 내지 C12의 알킬기 또는 C1 내지 C12의 알킬기로 치환된 C6 내지 C12의 아릴기이다.Wherein R 1 to preferably is an aryl group of C 6 to C 12 substituted with an alkyl group of C 1 to C 12 alkyl group or a C 1 to C 12 in.
상기 화학식 1로 표시되는 유기 술폰산은 직접 제조하거나 시판되는 것을 사용하고 상기 조건에 맞는 것으로 이 분야에서 공지된 것은 모두 사용 가능하다. 예를 들면, 메탄술폰산, 에탄술폰산, 프로판술폰산, 벤젠술폰산, 톨루엔 술폰산(4-메틸벤젠술폰산), 도데실벤젠 술폰산 등을 들 수 있으나, 이에 한정되는 것은 아니다.The organic sulfonic acid represented by the above formula (1) may be prepared directly or use a commercially available one, and any of those known in the art may be used. Examples thereof include, but are not limited to, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid (4-methylbenzenesulfonic acid), and dodecylbenzenesulfonic acid.
상기 유기 술폰산은 후술하는 알킬암모늄 플루오라이드와의 반응을 통해 불산(HF)과 바이플루오라이드 이온(HF2 -)을 생성한다. 이에 식각액의 pH는 낮아지고 생성된 HF와 HF2 -의 반응성이 높아져 티타늄막 식각 반응에 적극적으로 참여하여 식각속도를 향상시키는 역할을 한다. 또한 함께 적층되는 실리콘 산화막, 알루미늄막에 대한 보호효과를 가지는데 이는 유기 술폰산의 술폰산기가 실리콘 산화막과 알루미늄막 표면에 킬레이트 화합물로 피막을 형성함으로써 이루어진다.The organic sulfonic acid generates a hydrofluoric acid (HF) and a bifluoride ion (HF 2 - ) through a reaction with an alkylammonium fluoride to be described later. Thus, the pH of the etchant is lowered and the reactivity of HF and HF 2 - produced increases, thereby actively participating in the etching of the titanium film, thereby improving the etching rate. Also, it has a protective effect on the silicon oxide film and the aluminum film which are stacked together, because the sulfonic acid group of the organic sulfonic acid is formed by forming the film of the chelate compound on the silicon oxide film and the aluminum film surface.
이러한 유기 술폰산은 전체 조성물 100 중량% 내에서 0.1 내지 20 중량%로 사용되는 것이 바람직하며, 1 내지 10 중량%인 것이 더욱 바람직하다. 상기 유기 술폰산이 0.1 중량% 미만으로 사용되는 경우, 티타늄막의 식각속도가 현저히 감소하며, 20 중량%를 초과하는 경우, 식각액의 안정성 저하로 인해 색변화가 발생할 수 있으며 티타늄막의 식각속도 또한 감소되는 문제가 발생될 수 있다.The organic sulfonic acid is preferably used in an amount of 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on 100% by weight of the total composition. When the organic sulfonic acid is used in an amount of less than 0.1% by weight, the etching rate of the titanium film is remarkably decreased. When the organic sulfonic acid is used in an amount exceeding 20% by weight, the color change may occur due to the decrease in the stability of the etching solution. May occur.
본 발명에서의 알킬암모늄 플루오라이드는 하기 화학식 2로 표시되는 것을 특징으로 한다.The alkylammonium fluoride in the present invention is characterized by being represented by the following general formula (2).
(상기 화학식 2에서,(In the formula (2)
R2 내지 R5는 서로 같거나 다르며, 각각 독립적으로 C1 내지 C25의 알킬기 또는 C3 내지 C25의 사이클로알킬기이고,R 2 to R 5 are the same or different and are each independently a C 1 to C 25 alkyl group or a C 3 to C 25 cycloalkyl group,
X는 F- 또는 HF2 -이다)X is F - or HF 2 - a)
바람직하기로, 상기 R2 내지 R5는 서로 같거나 다르며, 각각 독립적으로 C1 내지 C10의 알킬기이다. Preferably, R 2 to R 5 are the same or different and are each independently a C 1 to C 10 alkyl group.
상기 화학식 2로 표시되는 알킬암모늄 플루오라이드는 직접 제조하거나 시판되는 것을 사용하고 상기 조건에 맞는 것으로 이 분야에서 공지된 것은 모두 사용 가능하다. 구체적인 예로는 테트라메틸암모늄플루오라이드, 테트라에틸암모늄플루오라이드, 테트라부틸암모늄플루오라이드, 테트라옥틸암모늄플루오라이드 및 이들의 조합으로 이루어진 군에서 선택되는 1종의 혼합물인 것을 특징으로 한다. The alkylammonium fluoride represented by the general formula (2) may be used either directly or commercially available, and any of those known in the art may be used. Specific examples thereof include a mixture of one selected from the group consisting of tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride, and combinations thereof.
또한, 상기 알킬암모늄 플루오라이드를 포함하는 본 발명의 티타늄막 식각액 조성물은 비수계로서 물을 포함하지 않는 것이 보다 바람직하다. In addition, the titanium film etchant composition of the present invention comprising the above alkylammonium fluoride is preferably a non-aqueous system which does not contain water.
상기 알킬암모늄 플루오라이드는 티타늄막 표면을 식각하는 역할을 하며 구체적으로 유기 용매 상에서 F- 또는 HF2 - 와 같은 불소 이온을 해리함으로써 티타늄막 식각 반응에 참여한다. The alkylammonium fluoride acts to etch the surface of the titanium film and specifically participates in the titanium film etching reaction by dissociating fluorine ions such as F - or HF 2 - on the organic solvent.
이러한 알킬암모늄 플루오라이드는 전체 조성물 100 중량% 내에서 0.1 내지 20 중량%로 사용되는 것이 바람직하며, 1 내지 10 중량%인 것이 더욱 바람직하다. 상기 알킬암모늄 플루오라이드가 0.1 중량% 미만으로 사용되는 경우, 원하는 티타늄막의 식각속도를 얻을 수 없으며, 20 중량%를 초과하는 경우, 실리콘 산화막, 알루미늄 막에 결함이 발생될 수 있으며, 알킬 플루오라이드 화합물이 석출될 수 있다.The alkylammonium fluoride is preferably used in an amount of 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on 100% by weight of the total composition. If the alkylammonium fluoride is used in an amount of less than 0.1 wt%, the etching rate of the desired titanium film can not be obtained. If the alkylammonium fluoride is used in an amount exceeding 20 wt%, defects may be generated in the silicon oxide film and the aluminum film, Can be precipitated.
본 발명에서의 유기 용매는 상기 언급한 바의 조성을 용해 또는 분산시키며 불소 이온에 의해 식각된 티타늄을 용해시켜 식각 반응이 보다 잘 이루어지도록 한다. 또한, 전술한 유기 술폰산과 알킬암모늄 플루오라이드가 반응하여 불산(HF)과 바이플루오라이드 이온(HF2 -)을 생성하는데 용매가 물인 경우 불산의 활성 증가 및 이로 인한 실리콘 산화막, 알루미늄막 공격이 발생하게 되는데 본 발명에서는 유기 용매를 사용하여 이러한 문제를 근본적으로 차단할 수 있다. The organic solvent in the present invention dissolves or disperses the above-mentioned composition and dissolves the titanium etched by the fluorine ion so that the etching reaction is more easily performed. In addition, when the organic sulfonic acid and alkyl ammonium fluoride react with each other to generate hydrofluoric acid (HF) and bifluoride ion (HF 2 - ), when the solvent is water, an increase in the activity of hydrofluoric acid and attack of silicon oxide film and aluminum film In the present invention, organic solvents can be used to fundamentally obviate such problems.
구체적으로, 상기 유기 용매는 설포란류, 케톤류 또는 이들의 조합이 바람직한데, 그 중에서도 특히, 설포란, 3-메틸설포란, 디벤조티오펜 5,5-디옥사이드 등의 설포란류; 메틸에틸케톤, 메틸부틸케톤, 메틸이소부틸케톤, 메틸펜틸케톤, 디메틸케톤, 디에틸케톤, 디이소부틸케톤, 사이클로헥사논, 아세토페논 등의 케톤류; 및 이들의 조합으로 이루어진 군에서 선택되는 1종을 사용하는 것이 효과적이다.Specifically, the organic solvent is preferably a sulfolane, a ketone or a combination thereof. Among them, sulfolane such as sulfolane, 3-methylsulfolane, dibenzothiophene 5,5-dioxide and the like; Ketones such as methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl pentyl ketone, dimethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and acetophenone; And a combination of these.
이러한 유기 용매는 전체 조성물 100 중량% 내에서 잔부로 사용되며 일례로 60 내지 98 중량%로 포함될 수 있다. 만약 유기 용매가 상기 범위 미만으로 사용되는 경우, 식각액 조성물의 용해도가 감소하며, 반대로 상기 범위를 초과하여 사용되는 경우, 식각된 티타늄이 효과적으로 제거되지 못하는 문제가 발생될 수 있다.
Such an organic solvent may be used as the remainder within 100% by weight of the total composition, for example 60 to 98% by weight. If the organic solvent is used in an amount less than the above range, the solubility of the etching solution composition is decreased. On the contrary, when the organic solvent is used in excess of the above range, the problem that the etched titanium can not be effectively removed may occur.
본 발명에서의 티타늄막은 티타늄막 또는 티타늄 합금막으로 목적에 따라 티타늄을 주성분으로 하고 다른 금속을 사용하여 합금으로 된 금속막을 포함하는 개념이다.
The titanium film in the present invention is a titanium film or a titanium alloy film, and includes a metal film mainly composed of titanium and alloyed with another metal, depending on purposes.
상기에서 언급된 티타늄막 식각방법은 당 업계에 통상적으로 알려진 방법에 의하여 수행될 수 있다. 예컨대, 침적, 분무, 또는 침적 및 분무를 이용한 방법 등이 사용될 수 있으며, 이 경우, 식각 조건으로서 온도는 대개 30 내지 80 ℃, 바람직하게는 50 내지 70 ℃이고, 침적, 분무, 또는 침적 및 분무 시간은 대개 30초 내지 10분, 바람직하게는 1분 내지 5분이다. 그러나, 이러한 조건은 엄밀하게 적용되지는 않으며, 당업자에 의해 용이하거나 적합한 조건으로 선택될 수 있다.
The above-mentioned titanium film etching method can be performed by a method commonly known in the art. For example, the method using deposition, spraying, or immersion and spraying may be used. In this case, the etching temperature is usually 30 to 80 캜, preferably 50 to 70 캜, and the deposition, spraying, The time is usually from 30 seconds to 10 minutes, preferably from 1 minute to 5 minutes. However, these conditions are not strictly applied and can be selected by those skilled in the art as being convenient or suitable.
본 발명에서 티타늄막과 함께 적층되며 기판 상에 존재하는 다른 막으로는 실리콘 산화막, 게이트 소재막 등이 있다. 실리콘 산화막은 게이트와 기판을 분리하는 절연체이며 주로 절연성이 있는 산화실리콘을 사용한다. 게이트 소재막은 금속막으로 이루어지며 게이트 단자를 형성하는 것으로 전도성이 있는 알루미늄으로 이루어진다.
In the present invention, other films that are laminated together with the titanium film and exist on the substrate include a silicon oxide film, a gate material film, and the like. The silicon oxide film is an insulator for separating the gate and the substrate, and mainly uses an insulating silicon oxide. The gate material film is made of a metal film and is made of conductive aluminum which forms a gate terminal.
본 발명에 따른 식각액 조성물은 반도체 장치 제조 공정에 있어 소스 전극, 게이트 전극, 드레인 전극이 형성된 반도체 기판 상에 티타늄막을 증착시킨 후 티타늄실리사이드막이 형성되면 상부의 잔존된 티타늄을 제거하기 위한 조성물이 필요하다. 이는 티타늄실리사이드의 상부에 잔존된 티타늄 및 산화티타늄으로 인해 발생될 수 있는 접촉 불량을 미연에 방지시킬 수 있다.The etching solution composition according to the present invention requires a composition for removing the remaining titanium on the top of a titanium silicide film after depositing a titanium film on a semiconductor substrate having a source electrode, a gate electrode, and a drain electrode formed in a semiconductor device manufacturing process . This can prevent in advance a contact failure which may be caused by titanium and titanium oxide remaining on the upper portion of the titanium silicide.
특히, 본 발명에 따른 식각액 조성물로 처리함으로써 제거가 요구되는 막질만을 선택적으로 제거할 수 있으며, 후속 공정의 신뢰성을 높여 반도체 장치의 품질을 향상시킬 수 있다. In particular, by treating with the etchant composition according to the present invention, it is possible to selectively remove only a film quality that is required to be removed, thereby improving the reliability of the subsequent process and improving the quality of the semiconductor device.
본 발명의 식각액 조성은 반도체 장치뿐 아니라 이를 포함하는 표시장치, MEMS 장치, 프린트 배선 기판 등의 제조공정에 사용 가능하다.
The composition of the etching solution of the present invention can be used not only for a semiconductor device but also for a manufacturing process of a display device, a MEMS device, a printed wiring board, etc. containing the same.
본 발명의 티타늄막 식각액 조성물은 우수한 티타늄막 식각속도 및 다른 막질에 대한 뛰어난 보호 효과를 가져 반도체 제조공정에 있어 향상된 식각 특성으로 생산성 및 신뢰성을 크게 향상시킬 수 있다.
The titanium film etchant composition of the present invention has excellent titanium film etch rate and excellent protective effect on other film quality, which can greatly improve productivity and reliability with improved etch characteristics in a semiconductor manufacturing process.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다.
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
실시예 1 내지 6 및 비교예 1 내지 11: 티타늄막 식각액 조성물의 제조Examples 1 to 6 and Comparative Examples 1 to 11: Preparation of Titanium Film Etchant Composition
하기 표 1 및 2에 기재된 성분 및 조성에 따라 티타늄막 식각액 조성물을 제조하였다.Titanium film etchant compositions were prepared according to the components and compositions listed in Tables 1 and 2 below.
(중량%)Furtherance
(weight%)
화합물Fluorine
compound
2) A-2: p-톨루엔술폰산(p-toluenesulfonic acid)
3) A-3: 옥살산(Oxalic acid)
4) A-4: 프탈산(Phthalic acid)
5) B-1: 테트라부틸암모늄플루오라이드(Tetrabutylammonium fluoride)
6) B-2: 테트라부틸암모늄바이플루오라이드(Tetramethylammonium Bifluoride)
7) C-1: 암모늄플루오라이드(Ammonium fluoride)
8) C-2: 플루오린화 규소산(Fluorosilicic acid)
9) D-1: 설포란(Sulfolane)
10) D-2: 2-헵타논(2-Heptanone)
11) D-3: 디메틸설폭사이드(Dimethylsulfoxide)
12) D-4: 테트라하이드로퍼퓨릴알코올(Tetrahydrofurfuryl alcohol)
13) D-5: 부틸아세테이트(n-Butylacetate)
14) D-6: 에틸렌글리콜(Ethylene glycol)1) A-1: Methanesulfonic acid
2) A-2: p-toluenesulfonic acid
3) A-3: Oxalic acid
4) A-4: Phthalic acid
5) B-1: Tetrabutylammonium fluoride
6) B-2: Tetramethylammonium Bifluoride
7) C-1: Ammonium fluoride
8) C-2: Fluorosilicic acid
9) D-1: Sulfolane
10) D-2: 2-Heptanone
11) D-3: Dimethylsulfoxide
12) D-4: Tetrahydrofurfuryl alcohol
13) D-5: Butyl acetate (n-Butylacetate)
14) D-6: Ethylene glycol
(중량%)Furtherance
(weight%)
화합물Fluorine
compound
2) A-2: p-톨루엔술폰산(p-toluenesulfonic acid)
3) A-3: 옥살산(Oxalic acid)
4) A-4: 프탈산(Phthalic acid)
5) B-1: 테트라부틸암모늄플루오라이드(Tetrabutylammonium fluoride)
6) B-2: 테트라부틸암모늄바이플루오라이드(Tetramethylammonium Bifluoride)
7) C-1: 암모늄플루오라이드(Ammonium fluoride)
8) C-2: 플루오린화 규소산(Fluorosilicic acid)
9) D-1: 설포란(Sulfolane)
10) D-2: 2-헵타논(2-Heptanone)
11) D-3: 디메틸설폭사이드(Dimethylsulfoxide)
12) D-4: 테트라하이드로퍼퓨릴알코올(Tetrahydrofurfuryl alcohol)
13) D-5: 부틸아세테이트(n-Butylacetate)
14) D-6: 에틸렌글리콜(Ethylene glycol)1) A-1: Methanesulfonic acid
2) A-2: p-toluenesulfonic acid
3) A-3: Oxalic acid
4) A-4: Phthalic acid
5) B-1: Tetrabutylammonium fluoride
6) B-2: Tetramethylammonium Bifluoride
7) C-1: Ammonium fluoride
8) C-2: Fluorosilicic acid
9) D-1: Sulfolane
10) D-2: 2-Heptanone
11) D-3: Dimethylsulfoxide
12) D-4: Tetrahydrofurfuryl alcohol
13) D-5: Butyl acetate (n-Butylacetate)
14) D-6: Ethylene glycol
실험예 1: 식각 특성 평가Experimental Example 1: Evaluation of etching characteristics
실리콘 웨이퍼 위에 티타늄막, 실리콘 산화막, 알루미늄막이 각각 단일막으로 증착된 웨이퍼를 준비하였다. 상기 기판을 2x2 cm 크기로 샘플링하여, 실시예 및 비교예에서 제조한 식각액 조성물로 상기 기판을 1 내지 5분간 침적 하였다. 물로 세정 후 Ellipsometer(SE-MG-1000)를 통해 각각의 막두께 변화를 아래와 같은 기준으로 판단하여 그 결과를 표 3에 표시하였다.A wafer on which a titanium film, a silicon oxide film, and an aluminum film were respectively deposited as a single film on a silicon wafer was prepared. The substrate was sampled at a size of 2 x 2 cm and the substrate was immersed for 1 to 5 minutes with the etchant composition prepared in Examples and Comparative Examples. After washing with water, the change in film thickness was judged by Ellipsometer (SE-MG-1000) based on the following criteria, and the results are shown in Table 3.
<기준><Standard>
(1) 티타늄막 식각속도(1) Titanium film etch rate
◎: 식각속도 100 Å/min 이상◎: etching rate 100 Å / min or more
○: 식각속도 50 내지 100 Å/min 미만?: Etching rate 50 to less than 100? / Min
△: 식각속도 50 Å/min 미만DELTA: etching rate less than 50 Å / min
×: 식각 안됨×: No etching
(2) 실리콘 산화막 변화(2) Silicon oxide film change
◎: 부식 전혀 없음◎: No corrosion at all
○: 부식 거의 없음○: almost no corrosion
△: 표면 거침 발생?: Surface roughness occurred
×: 에칭 발생×: Etching occurrence
(3) 알루미늄막 변화(3) Aluminum film change
◎: 부식 전혀 없음◎: No corrosion at all
○: 부식 거의 없음○: almost no corrosion
△: 표면 거침 발생?: Surface roughness occurred
×: 에칭 발생×: Etching occurrence
상기 표 3에 나타낸 바와 같이, 본 발명에서 제시하는 실시예 1 내지 6의 티타늄막 식각액은 비교예 1 내지 11과 비교하였을 때 티타늄막에 대한 식각 효과는 우수함과 동시에 패턴 상에 존재하는 다른 막인 실리콘 산화막, 알루미늄막에 대한 보호 효과도 탁월함을 확인하였다.As shown in Table 3, the titanium film etching solutions of Examples 1 to 6 of the present invention exhibited an excellent etching effect on the titanium film as compared with Comparative Examples 1 to 11, It was confirmed that the protective effect against the oxide film and the aluminum film was excellent.
구체적으로, 유기 술폰산 대신 유기산을 사용한 비교예 1의 경우, 티타늄막에 대한 식각 능력은 보였으나 다른 막질에 대한 보호 효과는 전혀 나타내지 못함을 확인하였다. Specifically, in the case of Comparative Example 1 using an organic acid instead of the organic sulfonic acid, the etching ability for the titanium film was observed, but it was confirmed that no protective effect for the other film was shown.
본 발명의 조성과 전혀 다른 무기산과 산화제를 사용한 비교예 2 및 3은 티타늄 식각 및 타층에 대한 보호에 부적합함을 보였다. Comparative Examples 2 and 3 using inorganic acids and oxidizing agents completely different from the composition of the present invention were found to be unsuitable for titanium etching and protection against other layers.
다음으로 다른 종류의 유기 용매를 사용한 비교예 4 내지 7의 경우, 하부막 보호 효과는 가지나 티타늄막 식각은 이루어지지 않음을 확인하였다. Next, in the case of Comparative Examples 4 to 7 using different kinds of organic solvents, it was confirmed that the protection effect of the lower film was good but the titanium film was not etched.
그리고 불소 화합물과 물로 이루어진 비교예 8 및 9는 티타늄막 식각은 가능하나 다른 막질에 대한 부식 억제는 이루어지지 않음을 확인할 수 있었다.In Comparative Examples 8 and 9 composed of a fluorine compound and water, it was confirmed that etching of the titanium film was possible but corrosion inhibition of other films was not achieved.
또한, 알킬암모늄 플루오라이드와 유기 용매만을 사용한 비교예 10 및 11의 경우 티타늄막 식각 반응은 진행되지 않으며 다른 막질에 결함 또한 발생하지 않음을 확인할 수 있었다. In addition, in the case of Comparative Examples 10 and 11 using only alkylammonium fluoride and an organic solvent, it was confirmed that the titanium film etching reaction did not proceed and defects did not occur in other films.
본 발명의 티타늄막 식각액 조성물은 우수한 티타늄막 식각속도 및 다른 막질에 대한 뛰어난 보호 효과를 가져 반도체 제조공정에 있어 향상된 식각 특성으로 생산성 및 신뢰성을 크게 향상시킬 수 있다. The titanium film etchant composition of the present invention has excellent titanium film etch rate and excellent protective effect on other film quality, which can greatly improve productivity and reliability with improved etch characteristics in a semiconductor manufacturing process.
Claims (8)
[화학식 1]
(상기 화학식 1에서,
R1은 C1 내지 C25의 알킬기, C3 내지 C25의 사이클로알킬기 또는 C6 내지 C20의 아릴기이고, 이때 아릴기는 분자 내 적어도 하나의 탄소 원자가 C1 내지 C12의 알킬기, C3 내지 C12의 사이클로알킬기기로 치환 또는 비치환된다)The titanium film etching liquid composition according to claim 1, wherein the organic sulfonic acid is represented by the following chemical formula 1:
[Chemical Formula 1]
(In the formula 1,
R 1 is C 1 to C 25 alkyl, C 3 to C 25 in the cycle of the alkyl group or a C 6 to C 20 aryl group, wherein the aryl group molecule at least one carbon atom C 1 to alkyl groups of C 12, C 3 To C 12 cycloalkyl group)
[화학식 2]
(상기 화학식 2에서,
R2 내지 R5는 서로 같거나 다르며, 각각 독립적으로 C1 내지 C25의 알킬기 또는 C3 내지 C25의 사이클로알킬기이고,
X는 F- 또는 HF2 -이다)The titanium film etching liquid composition according to claim 1, wherein the alkylammonium fluoride is represented by the following Chemical Formula 2:
(2)
(In the formula (2)
R 2 to R 5 are the same or different and are each independently a C 1 to C 25 alkyl group or a C 3 to C 25 cycloalkyl group,
X is F - or HF 2 - a)
유기 술폰산 0.1 내지 20 중량%,
알킬암모늄 플루오라이드 0.1 내지 20 중량%, 및
잔부로 유기 용매를 포함하는 것을 특징으로 하는 티타늄막 식각액 조성물.The titanium film etchant composition according to claim 1, wherein the titanium film etchant composition comprises 100 wt%
0.1 to 20% by weight of an organic sulfonic acid,
0.1 to 20% by weight of alkylammonium fluoride, and
And the remainder comprises an organic solvent.
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| KR20000028870A (en) | 1998-10-23 | 2000-05-25 | 구본준, 론 위라하디락사 | Method of manufacturing a substrate for electric device by using etchant and electric device having the substrate |
| KR20080015027A (en) * | 2005-06-13 | 2008-02-15 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | Compositions and methods for selective removal of metal or metal alloy after metal silicide formation |
| KR20110019604A (en) | 2009-08-20 | 2011-02-28 | 동우 화인켐 주식회사 | Etching solution composition for formation of metal line |
| KR20130008331A (en) * | 2011-07-12 | 2013-01-22 | 동우 화인켐 주식회사 | An etching solution composition for copper layer/titanium layer |
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| KR20000028870A (en) | 1998-10-23 | 2000-05-25 | 구본준, 론 위라하디락사 | Method of manufacturing a substrate for electric device by using etchant and electric device having the substrate |
| KR20080015027A (en) * | 2005-06-13 | 2008-02-15 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | Compositions and methods for selective removal of metal or metal alloy after metal silicide formation |
| KR20110019604A (en) | 2009-08-20 | 2011-02-28 | 동우 화인켐 주식회사 | Etching solution composition for formation of metal line |
| KR20130008331A (en) * | 2011-07-12 | 2013-01-22 | 동우 화인켐 주식회사 | An etching solution composition for copper layer/titanium layer |
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| WO2019145312A1 (en) * | 2018-01-25 | 2019-08-01 | Merck Patent Gmbh | Photoresist remover compositions |
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