CN110923713A - Etching liquid for copper-molybdenum and alloy films and preparation method thereof - Google Patents
Etching liquid for copper-molybdenum and alloy films and preparation method thereof Download PDFInfo
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- CN110923713A CN110923713A CN201911418246.XA CN201911418246A CN110923713A CN 110923713 A CN110923713 A CN 110923713A CN 201911418246 A CN201911418246 A CN 201911418246A CN 110923713 A CN110923713 A CN 110923713A
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- acid
- etching solution
- etching
- hydrogen peroxide
- alloy films
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- 238000005530 etching Methods 0.000 title claims abstract description 211
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000956 alloy Substances 0.000 title claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000007788 liquid Substances 0.000 title abstract description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 123
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 150000001412 amines Chemical class 0.000 claims abstract description 35
- 239000008139 complexing agent Substances 0.000 claims abstract description 33
- 230000007797 corrosion Effects 0.000 claims abstract description 33
- 238000005260 corrosion Methods 0.000 claims abstract description 33
- 239000003381 stabilizer Substances 0.000 claims abstract description 33
- 239000003112 inhibitor Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims description 26
- 230000000996 additive effect Effects 0.000 claims description 26
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 25
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 claims description 22
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 150000007524 organic acids Chemical group 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 10
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004220 glutamic acid Substances 0.000 claims description 6
- 235000013922 glutamic acid Nutrition 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000001477 organic nitrogen group Chemical group 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- 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 claims description 6
- OWRRVTILKGFXRZ-UHFFFAOYSA-N [2-aminoethyl(hydroxymethyl)amino]methanol Chemical compound NCCN(CO)CO OWRRVTILKGFXRZ-UHFFFAOYSA-N 0.000 claims description 5
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- 239000001530 fumaric acid Substances 0.000 claims description 5
- CFAZGYXPBDCSPT-UHFFFAOYSA-N 2-n-(2-aminoethyl)ethane-1,1,2-triamine Chemical compound NCCNCC(N)N CFAZGYXPBDCSPT-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- -1 amine compound Chemical class 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- SOIAEOTUSNFHMI-UHFFFAOYSA-N 2-(2-aminoethylamino)ethane-1,1-diol Chemical compound NCCNCC(O)O SOIAEOTUSNFHMI-UHFFFAOYSA-N 0.000 claims description 3
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- LOEUXOFEOFVSMW-UHFFFAOYSA-N CC(CNCC(O)O)N Chemical compound CC(CNCC(O)O)N LOEUXOFEOFVSMW-UHFFFAOYSA-N 0.000 claims description 3
- PUEPJJIDWJIGSZ-UHFFFAOYSA-N CCCC(N)NCC(O)O Chemical compound CCCC(N)NCC(O)O PUEPJJIDWJIGSZ-UHFFFAOYSA-N 0.000 claims description 3
- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 claims description 3
- ODBLHEXUDAPZAU-FONMRSAGSA-N Isocitric acid Natural products OC(=O)[C@@H](O)[C@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-FONMRSAGSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- VRKRVDQKHBBOJE-UHFFFAOYSA-N N"-(2-aminoethyl)methanetriamine Chemical compound NCCNC(N)N VRKRVDQKHBBOJE-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 claims description 3
- POHHDAXTXGZMDA-UHFFFAOYSA-N [H]NC([H])(C([H])([H])[H])C([H])([H])NC(N([H])[H])N([H])[H] Chemical compound [H]NC([H])(C([H])([H])[H])C([H])([H])NC(N([H])[H])N([H])[H] POHHDAXTXGZMDA-UHFFFAOYSA-N 0.000 claims description 2
- VTFCXBBNRRGNDC-UHFFFAOYSA-N 3-N',3-N'-diaminohexane-3,3-diamine Chemical compound CCCC(N)(CC)N(N)N VTFCXBBNRRGNDC-UHFFFAOYSA-N 0.000 claims 1
- OUKGZNBWBOEIAO-UHFFFAOYSA-N CC(CNCC(N)N)N Chemical compound CC(CNCC(N)N)N OUKGZNBWBOEIAO-UHFFFAOYSA-N 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 23
- 150000004706 metal oxides Chemical class 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 22
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 21
- 229910001431 copper ion Inorganic materials 0.000 description 21
- 239000000758 substrate Substances 0.000 description 20
- 238000001878 scanning electron micrograph Methods 0.000 description 15
- 239000010949 copper Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 239000001384 succinic acid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 3
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 3
- VAOAXFLXWLZYKU-UHFFFAOYSA-N CCNCCN(N)N Chemical compound CCNCCN(N)N VAOAXFLXWLZYKU-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- LJXQPZWIHJMPQQ-UHFFFAOYSA-N pyrimidin-2-amine Chemical compound NC1=NC=CC=N1 LJXQPZWIHJMPQQ-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- MMQFYDQGJNKDBV-UHFFFAOYSA-N 1h-imidazole;1h-indole Chemical compound C1=CNC=N1.C1=CC=C2NC=CC2=C1 MMQFYDQGJNKDBV-UHFFFAOYSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- ULWQSADGNFQTFS-UHFFFAOYSA-N CCC(CC)(N)NCC(N)N Chemical compound CCC(CC)(N)NCC(N)N ULWQSADGNFQTFS-UHFFFAOYSA-N 0.000 description 1
- UEFGXZYNDWFTAN-UHFFFAOYSA-N CCC(N)NC(N)N Chemical compound CCC(N)NC(N)N UEFGXZYNDWFTAN-UHFFFAOYSA-N 0.000 description 1
- LXYHKWPCVLLTNB-UHFFFAOYSA-N CCCC(N)NCC(N)N Chemical compound CCCC(N)NCC(N)N LXYHKWPCVLLTNB-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- AKNQMEBLVAMSNZ-UHFFFAOYSA-N azaconazole Chemical compound ClC1=CC(Cl)=CC=C1C1(CN2N=CN=C2)OCCO1 AKNQMEBLVAMSNZ-UHFFFAOYSA-N 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
Images
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
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention provides an etching solution for copper-molybdenum and alloy films and a preparation method thereof, wherein the etching solution comprises the following components: hydrogen peroxide, a hydrogen peroxide stabilizer, an amine pH regulator, a complexing agent, a metal corrosion inhibitor and the balance of water; the amine pH regulator is a compound shown as a formula 1 and/or a formula 2, wherein R1、R4Independently selected from C1～4Alkylene radical, R2、R3、R5、R6Independently selected from single bond or C2～4An alkylene group. The etching liquid can realize excellent etching precision, does not damage a metal oxide IGZO film layer, can realize the upgrading of an IGZO product from a 6Mask process to a 5Mask process, and is beneficial to reducing the manufacturing cost of a display product and improving the resolution of the display product.
Description
Technical Field
The invention relates to an etching solution, in particular to an etching solution for copper-molybdenum and alloy films and a preparation method thereof, and belongs to the technical field of etching.
Background
In the existing TFT array production process, aiming at the requirements of large size, high resolution and driving frequency of liquid crystal display products such as televisions and the like, the problem of resistance/capacitance time delay in a TFT array substrate is mostly solved by etching a copper-molybdenum metal layer by using etching liquid to generate a metal layer with a specific pattern.
In the etching process, in order to avoid corrosion of the metal oxide semiconductor by the etching solution, an etching barrier layer semiconductor structure is generally adopted, namely, a semiconductor protection layer is added to ensure that the metal oxide semiconductor is not influenced by the etching solution, but the semiconductor protection layer not only increases the manufacturing cost and the manufacturing period of the display product, but also has negative influence on the resolution of the display product.
Disclosure of Invention
The etching liquid for the copper-molybdenum and alloy films provided by the invention can realize excellent etching precision, does not damage the metal oxide IGZO film layer, and is beneficial to reducing the manufacturing cost of display products and improving the resolution of the display products.
The invention also provides a preparation method of the etching solution for the copper-molybdenum and alloy films, which is simple and feasible and can efficiently finish the etching solution with excellent etching performance and no damage to the metal oxide IGZO film layer.
The invention provides an etching solution for copper-molybdenum and alloy films, which comprises the following components: hydrogen peroxide, a hydrogen peroxide stabilizer, an amine pH regulator, a complexing agent, a metal corrosion inhibitor and the balance of water; the amine pH regulator is a compound shown in a formula 1 and/or a formula 2,
wherein R is1、R4Independently selected from C1～4Alkylene radical, R2、R3、R5、R6Independently selected from single bond or C2～4An alkylene group.
The etching solution for the copper-molybdenum and alloy films comprises the following components in percentage by mass: 6-15% of hydrogen peroxide, 0.01-5% of hydrogen peroxide stabilizer, 1-10% of amine pH regulator, 0.01-10% of complexing agent, 0.01-5% of metal corrosion inhibitor and the balance of water.
The etching solution for copper molybdenum and alloy films as described above, wherein the amine pH adjuster is one or more selected from N, N-dimethylolethylenediamine, N-dimethylolepropylenediamine, N-dihydroxyethylpropylenediamine, N-dihydroxyethylethylenediamine, N-dihydroxyethylbutanediamine, N-diaminomethylethylenediamine, N-diaminomethylpropylenediamine, N-diaminoethylethylenediamine, N-diaminoethylethylenediamine, and N, N-diaminoethylethylenediamine.
The etching solution for the copper molybdenum and alloy film is characterized in that the hydrogen peroxide stabilizer is an organic acid and/or an organic amine compound.
The etching solution for the copper-molybdenum and alloy films is characterized in that the hydrogen peroxide stabilizer is a mixture of organic acid and phenylurea.
The etching solution for copper molybdenum and alloy films is characterized in that the complexing agent is organic acid and/or organic nitrogen-containing compound.
The etching solution for copper molybdenum and alloy films as described above, wherein the organic acid is selected from one or more of acetic acid, oxalic acid, propionic acid, succinic acid, malonic acid, glutaric acid, adipic acid, α, ω -diamine acetic acid, α, ω -diamine succinic acid, α, ω -diamine propionic acid, 1, 2-diaminopropane tetraacetic acid, citric acid, isocitric acid, fumaric acid, maleic acid, glutamic acid, tartaric acid, batholinedisulfonic acid, and derivatives thereof;
the organic nitrogen-containing compound is selected from one or more of bipyridyl, phenanthroline and derivatives thereof.
The etching solution for copper molybdenum and alloy films as described above, wherein the metal corrosion inhibitor is one or more selected from aliphatic sulfur-containing compounds, aliphatic nitrogen-containing compounds and heterocyclic compounds.
The etching solution for the copper-molybdenum and alloy films further comprises an additive; the additive comprises the following components in percentage by mass: 0.01-10% of hydrogen peroxide stabilizer, 5-15% of amine pH regulator, 1-10% of complexing agent, 0.01-5% of metal corrosion inhibitor and the balance of water.
The invention also provides a preparation method of the etching solution for the copper molybdenum and alloy film, which comprises the step of mixing hydrogen peroxide, a hydrogen peroxide stabilizer, an amine pH regulator, a complexing agent, a metal corrosion inhibitor and water to obtain the etching solution for the copper molybdenum and alloy film.
The etching liquid for the copper-molybdenum and alloy films can realize excellent etching precision and ensure CD LOSS and Taper performances in etching treatment through mutual cooperation of the components, does not damage a metal oxide IGZO film layer, can realize TFT array substrate production through a semiconductor structure (for example, back channel etching) without etching a barrier layer, reduces the manufacturing cost and the manufacturing period of the TFT array substrate, and can improve the resolution of a display product; in addition, the etching solution for the copper-molybdenum and alloy films does not contain fluorine ions and phosphorus, and is environment-friendly.
Drawings
FIG. 1a is an SEM image of a cross section of an etching solution of example 1 of the present invention at an etching time of 150 s;
FIG. 1b is a SEM image of the surface of an etching solution of example 1 of the present invention at an etching time of 150 s;
FIG. 2a is an SEM image of a cross section of an etching solution of example 1 of the present invention at an etching time of 240 s;
FIG. 2b is a SEM image of the surface of the etching solution of example 1 of the present invention at an etching time of 240 s;
FIG. 3a is an SEM image of a cross section of an etching solution of example 2 of the present invention at an etching time of 240 s;
FIG. 3b is a SEM image of the surface of the etching solution of example 2 of the present invention at an etching time of 240 s;
FIG. 4a is an SEM photograph of a cross-section of an etching solution of example 3 of the present invention during an etching time of 240 s;
FIG. 4b is a SEM image of the surface of the etching solution of example 3 of the present invention at an etching time of 240 s;
FIG. 5 is an SEM photograph of a cross section of an etching solution of comparative example 1 of the present invention at an etching time of 240 s;
FIG. 6a is an SEM image of a cross section of example 1 of the present invention etched at 10000ppm of copper ions for 240 s;
FIG. 6b is an SEM image of the surface of example 1 of the present invention etched at 10000ppm of copper ion for 240 s.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an etching solution for copper-molybdenum and alloy films, which comprises the following components in percentage by mass: hydrogen peroxide, hydrogen peroxide stabilizer, amine pH regulator, complexing agent, metal corrosion inhibitor and the balance of water,
wherein R is1、R4Independently selected from C1～4Alkylene radical, R2、R3、R5、R6Independently selected from single bond or C2～4An alkylene group.
The hydrogen peroxide has excellent oxidizing ability and can oxidize the copper-molybdenum metal layer to form metal ions, so that the copper-molybdenum metal layer is etched.
Generally, in the etching process, the temperature of the etching liquid system continuously rises along with the oxidation of the copper-molybdenum metal layer by hydrogen peroxide, so that the hydrogen peroxide is further rapidly decomposed to influence the etching precision and the etching efficiency, and the metal oxide IGZO film layer is corroded and damaged in a high-temperature oxidation system.
According to the technical scheme provided by the invention, the specific auxiliary agents (the hydrogen peroxide stabilizer, the amine pH regulator, the complexing agent and the metal corrosion inhibitor) are added into the hydrogen peroxide solution, so that the stabilization effect on the hydrogen peroxide is enhanced, the hydrogen peroxide is prevented from being rapidly decomposed, the accurate etching is favorably realized, a safe environment is provided for the metal oxide IGZO film layer, the metal oxide IGZO film layer is prevented from being damaged, the integrity of the metal oxide IGZO film layer is ensured, an etching barrier layer semiconductor structure is not required to be adopted in the preparation process of the TFT array substrate, and the IGZO product can be upgraded from a 6Mask process to a 5Mask process.
According to the etching solution disclosed by the invention, in the process of etching the copper-molybdenum layer by using hydrogen peroxide, the hydrogen peroxide stabilizer, the amine pH regulator, the complexing agent and the metal corrosion inhibitor are cooperated with one another, so that a safe environment can be provided for the metal oxide IGZO film layer, the damage of the etching solution to the metal oxide IGZO film layer is avoided, and the electrical characteristics of the metal oxide IGZO film layer are ensured.
Because the etching solution disclosed by the invention has no corrosion damage to the metal oxide IGZO film layer, when the etching solution disclosed by the invention is used for etching the copper-molybdenum metal layer, a semiconductor structure without an etching barrier layer (such as back channel etching) can be adopted to realize the production of the TFT array substrate, so that the photomask, materials and energy are reduced, the process flow is simplified, and the manufacturing cost and the manufacturing period of the TFT array substrate are effectively reduced; and because the TFT array substrate does not contain an etching barrier layer, the working performance of the TFT array substrate is further improved, and the resolution of a display product is improved.
In addition, the specific amine pH regulator and the metal corrosion inhibitor are also beneficial to improving the etching precision. Specifically, the amine pH regulator can generate Van der Waals force with metal copper and act together with a flow field to regulate the Taper angle, so that the process requirement is met; compared with copper etching, molybdenum etching difficulty is higher, so that the metal corrosion inhibitor can inhibit copper etching speed, keep copper metal and molybdenum metal to have close etching speed, and avoid molybdenum layer trailing, thereby improving etching precision and presenting perfect etching effect.
In a specific implementation mode, the etching solution comprises the following components in percentage by mass: 6-15% of hydrogen peroxide, 0.01-5% of hydrogen peroxide stabilizer, 1-10% of amine pH regulator, 0.01-10% of complexing agent, 0.01-5% of metal corrosion inhibitor and the balance of water.
The amine pH regulator is used for controlling the pH value of an etching system to be 3-6. The inventor researches and discovers that when the pH value of an etching system is too low, the etching speed of a copper layer can be accelerated, so that the difference between the etching speeds of the copper layer and a molybdenum layer is too obvious, and the phenomenon of molybdenum residue or molybdenum layer tailing is easily caused; and the pH value is too high, so that the decomposition rate of hydrogen peroxide is accelerated, and the etching effect is influenced. In addition, the amine pH regulator disclosed by the invention cannot damage the metal oxide IGZO film layer, and can cooperate with other components to provide a safe environment for the metal oxide IGZO film layer in an etching process, so that the electrical properties of the metal oxide IGZO film layer are ensured.
Specifically, the amine pH adjuster of the present invention is one or more selected from N, N-dimethylolethylenediamine, N-dimethylolepropylenediamine, N-dihydroxyethylpropylenediamine, N-dihydroxyethylethylenediamine, N-dihydroxyethylbutanediamine, N-diaminomethylethylenediamine, N-diaminomethylpropanediamine, N-diaminoethylethylpropanediamine, N-diaminoethylethylenediamine, N-diaminoethylbutanediamine, and derivatives thereof. Of course, if the amine-based pH adjuster in the etching liquid is two or more of the above compounds, the present invention does not particularly limit the ratio between the compounds.
The hydrogen peroxide stabilizer can inhibit the rapid decomposition of hydrogen peroxide and keep the temperature of an etching liquid system in a relatively normal state, thereby being beneficial to ensuring the etching efficiency and the etching effect. Specifically, the hydrogen peroxide stabilizer of the present invention may be selected from organic acids and/or organic amine compounds, wherein the organic acids may be citric acid, tartaric acid, gluconic acid, glycolic acid, oxalic acid, malonic acid, succinic acid, malic acid, p-hydroxybenzene sulfonic acid, succinic acid, etc. The inventors surprisingly found that when the hydrogen peroxide stabilizer is a mixture of phenylurea and an organic acid, the integrity of the metal oxide IGZO film layer during etching is extremely excellent, and it is assumed that the hydrogen peroxide stabilizer of the composition may have a protective effect on the metal oxide IGZO film layer.
The complexing agent can effectively combine copper ions in the etching process, and avoids accelerating the decomposition of hydrogen peroxide due to overhigh concentration of the copper ions. The complexing agent can be organic acid and/or organic nitrogen-containing compound, and specifically, the lone electron pair in the complexing agent completes the complexing with the copper ion through forming a covalent bond II with an outer empty orbit of the copper ion, so that the catalytic decomposition of the copper ion on hydrogen peroxide is inhibited, the stability of the hydrogen peroxide is improved, and the excellent etching precision is favorably realized.
In one embodiment, the organic acid in the complexing agent may be selected from the group consisting of acetic acid, oxalic acid, propionic acid, succinic acid, malonic acid, glutaric acid, adipic acid, α, ω -diamine acetic acid, α, ω -diamine succinic acid, α, ω -diamine propionic acid, 1, 2-diaminopropane tetraacetic acid, citric acid, isocitric acid, fumaric acid, maleic acid, glutamic acid, tartaric acid, bathonelingdisulfonic acid, and salts thereof, the organic nitrogen-containing compound in the complexing agent may be selected from the group consisting of bipyridine, phenanthroline, and derivatives thereof, and if the complexing agent in the etching solution is two or more of the above compounds, the ratio between the compounds is not particularly limited in the present invention.
The metal corrosion inhibitor is selected from one or more of aliphatic sulfur-containing compounds, aliphatic nitrogen-containing compounds and heterocyclic compounds, is mainly used for reducing the etching speed of copper metal, avoids the phenomenon of hydrogen peroxide accelerated decomposition caused by overhigh concentration of copper ions, and further ensures the stability of hydrogen peroxide.
Specifically, the compound may be one or more of 1-phenyl-5-mercaptotetrazole, tetrazole, benzotriazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-aminopyrimidine, azoconazole, 3-amino-1, 2,4 triazole, hydroxybenzotriazole, 5-aminotetrazole, imidazole indole, pyrazole, purine, pyridine, pyrrole and pyrrolidine. If the metal corrosion inhibitor in the etching solution is two or more of the above compounds, the ratio between the compounds is not particularly limited in the present invention.
It is worth noting that during the etching process, the copper ion concentration in the etching liquid system needs to be monitored, and when the copper ion concentration in the etching liquid system increases by 100ppm, the additive needs to be added into the etching liquid system.
The additive is similar to the etching liquid in composition, and specifically comprises 0.01-10% of hydrogen peroxide stabilizer, 5-15% of amine pH regulator, 1-10% of complexing agent, 0.01-5% of metal corrosion inhibitor and the balance of water by mass percentage. The specific selection of various functional components is the same as above, and is not described herein again.
In the adding process, the adding amount of the additive is determined based on the original volume of the etching solution, and the volume of the additive is generally controlled to be 0.2 percent of the original volume of the etching solution. Wherein, the original volume of the etching liquid refers to the volume of the etching liquid when the etching treatment is started.
The second aspect of the present invention provides a method for preparing the etching solution, comprising: hydrogen peroxide, hydrogen peroxide stabilizer, amine pH regulator, complexing agent, metal corrosion inhibitor and water are mixed and stirred to obtain the etching solution for copper-molybdenum and alloy films.
The mass percentage of each component in the etching solution is the same as that described above, and the details are not repeated here.
Specifically, the hydrogen peroxide and the water can be mixed firstly, and then the hydrogen peroxide stabilizer, the amine pH regulator, the complexing agent and the metal corrosion inhibitor are added into the mixed system respectively, wherein the adding sequence of the hydrogen peroxide stabilizer, the amine pH regulator, the complexing agent and the metal corrosion inhibitor is not limited.
The preparation method of the etching liquid has low process difficulty, and can realize the purpose of obtaining the etching liquid with the protective effect on the metal oxide IGZO film layer in a safe and efficient manner.
In order to ensure the solubility of each component in the etching solution, the components can be mixed at about 30-35 ℃ to further ensure the performance of the etching solution.
Further, the etching process also comprises the step of adding the additive into the etching liquid system.
Wherein the composition of the additive is the same as above. The invention does not limit the adding mode of the additive, and can complete the preparation of the additive in advance and then add the additive into the etching liquid system; or the components of the additive can be added into the etching liquid system respectively.
Hereinafter, the etching liquid of the present invention will be described in detail by way of specific examples.
Example 1
The etching solution of the embodiment comprises the following components in percentage by mass:
10 percent of hydrogen peroxide
Hydrogen peroxide stabilizer: 1.5 percent of malonic acid, 2.2 percent of succinic acid and 0.2 percent of phenylurea
Amine pH regulators: 2.8 percent of N, N-diaminoethyl ethylenediamine
Complexing agent: 3.66 percent of glutamic acid
Metal corrosion inhibitor: 2-aminopyrimidine 0.05%
Water: 79.59 percent
The above components were mixed at 32 ℃ and stirred to obtain the etching solution of this example.
The additive of the etching liquid comprises the following components in percentage by mass:
hydrogen peroxide stabilizer: 4.88 percent of malonic acid, 4.57 percent of succinic acid and 0.2 percent of phenylurea
Amine pH regulators: 6.53 percent of N, N-diaminoethyl ethylenediamine
Complexing agent: glutamic acid 5.58%
Metal corrosion inhibitor: 2-aminopyrimidine 0.05%
Water: 78.19 percent
The components are mixed and stirred at 32 ℃ to obtain the additive of the etching solution of the embodiment.
Example 2
The etching solution of the embodiment comprises the following components in percentage by mass:
12 percent of hydrogen peroxide
Hydrogen peroxide stabilizer: p-hydroxybenzenesulfonic acid 0.3%, succinic acid 2.16%, phenylurea 0.15% amine pH regulator: 2.12 percent of N, N-dihydroxyethyl propane diamine
Complexing agent: 3.66 percent of malonic acid
Metal corrosion inhibitor: 0.04% of 3-amino-1, 2,4 triazole
Water: 79.57 percent
The above components were mixed at 32 ℃ and stirred to obtain the etching solution of this example.
The additive of the etching liquid comprises the following components in percentage by mass:
hydrogen peroxide stabilizer: 6.54 percent of succinic acid and 0.2 percent of phenylurea
Amine pH regulators: 7.24 percent of N, N-dihydroxyethyl propane diamine
Complexing agent: 3.75 percent of glutamic acid
Metal corrosion inhibitor: 0.1 percent of 3-amino-1, 2,4 triazole
Water: 82.17 percent
The components are mixed and stirred at 32 ℃ to obtain the additive of the etching solution of the embodiment.
Example 3
The etching solution of the embodiment comprises the following components in percentage by mass:
12 percent of hydrogen peroxide
Hydrogen peroxide stabilizer: malic acid 3.96%, phenylurea 0.1%
Amine pH regulators: 2.97 percent of N, N-dimethylol ethylenediamine
Complexing agent: malonic acid 0.81%
Metal corrosion inhibitor: 0.03 percent of 5-aminotetrazole
Water: 80.13 percent
The above components were mixed at 32 ℃ and stirred to obtain the etching solution of this example.
The additive of the etching liquid comprises the following components in percentage by mass:
hydrogen peroxide stabilizer: malic acid 6.95%, phenylurea 0.3%
Amine pH regulators: 7.89 percent of N, N-dimethylol ethylenediamine
Complexing agent: 4.17 percent of malonic acid
Metal corrosion inhibitor: 0.1 percent of 5-aminotetrazole
Water: 80.59 percent
The components are mixed and stirred at 32 ℃ to obtain the additive of the etching solution of the embodiment.
Comparative example 1
The etching solution of the comparative example comprises the following components in percentage by mass:
10 percent of hydrogen peroxide
2 percent of nitric acid
Hydrogen peroxide stabilizer: 1.5 percent of malonic acid, 2.2 percent of succinic acid and 0.2 percent of phenylurea
pH regulator: 3.35 percent of dimethylethanolamine
Complexing agent: fumaric acid 4.38%
Metal corrosion inhibitor: 0.05 percent of benzotriazole
Water: 76.32 percent
The above components were mixed at 32 ℃ and stirred to obtain the etching solution of this example.
The additive of the etching liquid of the comparative example comprises the following components in percentage by mass:
hydrogen peroxide stabilizer: 4.88 percent of malonic acid, 4.57 percent of succinic acid and 0.2 percent of phenylurea
Amine pH regulators: dimethylethanolamine 6.94%
Complexing agent: fumaric acid 5.50%
Metal corrosion inhibitor: 1.00 percent of benzotriazole
Water: 76.91 percent
The components are mixed and stirred at 32 ℃ to obtain the additive of the etching solution of the embodiment.
Test example 1
After a copper film (6000A) and a molybdenum film (150A) are plated on a glass substrate, a resist is applied, exposed and developed to form a desired pattern. 4 substrates were suspended and immersed in 4 containers of the etching solution of example 1, which were magnetically stirred, at 32 ℃ for 190s, 210s, 240s, and 270s, respectively. After the etching was completed, the substrate was taken out, washed with water and dried, and the etching result was observed with an electron microscope, and the results are shown in table 1. In the etching process, when the concentration of copper ions is increased by 100ppm, an additive with the original volume of 0.2 percent of the etching solution is added into an etching solution system.
Meanwhile, 4 substrates were suspended and immersed in the etching solutions of examples 2 to 3 and comparative example 1, respectively, with magnetic stirring at 32 ℃ for 240 s. After the etching was completed, the substrate was taken out, washed with water and dried, and the etching result was observed with an electron microscope, and the results are shown in table 2. In the etching process, when the concentration of copper ions is increased by 100ppm, an additive with the original volume of 0.2 percent of the etching solution is added into an etching solution system.
TABLE 1
| Etching time (S) | 190 | 210 | 240 | 270 |
| Taper(°) | 39 | 43 | 45 | 47 |
| CD LOSS(um) | 0.65 | 0.7 | 0.67 | 0.77 |
TABLE 2
| Taper(°) | CD LOSS(um) | Chamfering | Metal residue | |
| Comparative example 1 | 58 | 1.1 | Is provided with | Is free of |
| Example 2 | 43 | 0.75 | Is free of | Is free of |
| Example 3 | 37 | 0.75 | Is free of | Is free of |
FIG. 1a is an SEM image of a cross section of an Etching solution of example 1 of the present invention at an Etching time of 150s, FIG. 1b is an SEM image of a surface of an Etching solution of example 1 of the present invention at an Etching time of 150s, and metal residue can be seen in Just Etching;
FIG. 2a is an SEM image of a cross section of the etching solution of example 1 of the present invention at an etching time of 240s, and FIG. 2b is an SEM image of a surface of the etching solution of example 1 of the present invention at an etching time of 240s, and it can be seen that CD LOSS Taper is good and no metal remains;
FIG. 3a is an SEM photograph of a cross section of an etching solution of example 2 of the present invention at an etching time of 240s, and FIG. 3b is an SEM photograph of a surface of the etching solution of example 2 of the present invention at an etching time of 240 s;
FIG. 4a is an SEM photograph of a cross section of an etching solution of example 3 of the present invention at an etching time of 240s, and FIG. 4b is an SEM photograph of a surface of the etching solution of example 3 of the present invention at an etching time of 240 s;
FIG. 5 is an SEM photograph of a cross section of an etching solution of comparative example 1 of the present invention at an etching time of 240 s;
as can be seen from tables 1 and 2 and the figures, the etching solution of the invention has excellent etching precision, while the etching solution of the comparative example has poor etching performances such as chamfering and unilateral line width loss of the metal layer after etching.
Test example 2
10000ppm of copper ions were added to the etching solution of example 1, and the following test was performed.
After a copper film (6000A) and a molybdenum film (150A) are plated on a glass substrate, a resist is applied, exposed and developed to form a desired pattern. And (3) respectively suspending and soaking 4 substrates in 4 containers of the etching solution stirred by magnetic force at 32 ℃, and controlling the etching time to be 190s, 210s, 240s and 270 s. After the etching was completed, the substrate was taken out, washed with water and dried, and the etching result was observed with an electron microscope, and the results are shown in table 3. In the etching process, when the concentration of copper ions is increased by 100ppm, an additive with the original volume of 0.2 percent of the etching solution is added into an etching solution system.
TABLE 3
| Etching time (S) | 190 | 210 | 240 | 270 |
| Taper(°) | 44 | 42 | 43 | 45 |
| CD LOSS(um) | 0.69 | 0.74 | 0.76 | 0.83 |
As can be seen from Table 3, the etching solution of the present invention can achieve precise etching even under conditions of high copper ion concentration.
FIG. 6a is an SEM image of a cross section of example 1 of the present invention at 10000ppm of copper ion for 240s, and FIG. 6b is an SEM image of a surface of example 1 of the present invention at 10000ppm of copper ion for 240s, and it can be seen that Taper and CD LOSS are both good at high Cu ion.
Test example 3
Taking 4 parts of the etching solution of example 1, wherein the first part is the No. 1 etching solution, adding 500ppm of copper ions into the second part of the etching solution to obtain the No. 2 etching solution, adding 6000ppm of copper ions into the third part of the etching solution to obtain the No. 3 etching solution, and adding 10000ppm of copper ions into the fourth part of the etching solution to obtain the No. 4 etching solution.
The substrate with the exposed metal oxide IGZO film layer is respectively soaked in No. 1-4 etching solution, after being soaked for 10Min at 32 ℃, the substrate is taken out, washed and dried, and the metal oxide IGZO film layer is detected by an electron microscope and an X-ray photoelectron spectrum analyzer (two soaking tests are carried out under the same condition), and the results are shown in tables 4-5. In the etching process, when the concentration of copper ions is increased by 100ppm, an additive with the original volume of 0.2 percent of the etching solution is added into an etching solution system.
Meanwhile, the same operation was performed on the etching solution of comparative example 1 according to the above method, and the results are shown in Table 6.
Meanwhile, an IGZO film soaking experiment was performed on the etching solution of example 2/3 in accordance with the above method, and the results are shown in Table 7.
TABLE 4
TABLE 5
TABLE 6
TABLE 7
As can be seen from tables 4, 5, 6 and 7: the etching liquid provided by the invention has almost no damage to the metal oxide IGZO film layer, so that the TFT array substrate can be produced by etching the metal layer by using the etching liquid provided by the invention with a semiconductor structure (for example, back channel etching) without etching a barrier layer, the manufacturing cost and the manufacturing period of the TFT array substrate are reduced, and the resolution of a display product can be improved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The etching solution for the copper-molybdenum and alloy films is characterized by comprising the following components: hydrogen peroxide, a hydrogen peroxide stabilizer, an amine pH regulator, a complexing agent, a metal corrosion inhibitor and the balance of water; the amine pH regulator is a compound shown in a formula 1 and/or a formula 2,
wherein R is1、R4Independently selected from C1～4Alkylene radical, R2、R3、R5、R6Independently selected from single bond or C2～4An alkylene group.
2. The etching solution for copper molybdenum and alloy films according to claim 1, which comprises the following components in percentage by mass: 6-15% of hydrogen peroxide, 0.01-5% of hydrogen peroxide stabilizer, 1-10% of amine pH regulator, 0.01-10% of complexing agent, 0.01-5% of metal corrosion inhibitor and the balance of water.
3. The etching solution for copper molybdenum and alloy films according to any one of claims 1 to 2, wherein the amine-based pH adjuster is one or more selected from N, N-dimethylolethylenediamine, N-dimethylolepropylenediamine, N-dihydroxyethylpropylenediamine, N-dihydroxyethylethylenediamine, N-dihydroxyethylbutanediamine, N-diaminomethylethylenediamine, N-diaminomethylpropylenediamine, N-diaminoethylpropylenediamine, N-diaminoethylethylenediamine, and N, N-diaminoethylbutanediamine.
4. The etching solution for copper molybdenum and alloy films according to any one of claims 1 to 2, wherein the hydrogen peroxide stabilizer is an organic acid and/or an organic amine compound.
5. The etching solution for copper molybdenum and alloy films according to claim 4, wherein the hydrogen peroxide stabilizer is a mixture of organic acid and phenylurea.
6. The etching solution for copper molybdenum and alloy films according to any one of claims 1 to 2, wherein the complexing agent is an organic acid and/or an organic nitrogen-containing compound.
7. The etching solution for copper molybdenum and alloy films according to claim 6, wherein the organic acid is selected from one or more of acetic acid, oxalic acid, propionic acid, succinic acid, malonic acid, glutaric acid, adipic acid, α, ω -diamine acetic acid, α, ω -diamine succinic acid, α, ω -diamine propionic acid, 1, 2-diaminopropane tetraacetic acid, citric acid, isocitric acid, fumaric acid, maleic acid, glutamic acid, tartaric acid, bathoneldiphonic acid, and derivatives thereof;
the organic nitrogen-containing compound is selected from one or more of bipyridyl, phenanthroline and derivatives thereof.
8. The etching solution for copper molybdenum and alloy films according to any one of claims 1 to 2, wherein the metal corrosion inhibitor is one or more selected from aliphatic sulfur-containing compounds, aliphatic nitrogen-containing compounds and heterocyclic compounds.
9. The etching solution for copper molybdenum and alloy films according to claim 1, further comprising an additive; the additive comprises the following components in percentage by mass: 0.01-10% of hydrogen peroxide stabilizer, 5-15% of amine pH regulator, 1-10% of complexing agent, 0.01-5% of metal corrosion inhibitor and the balance of water.
10. A preparation method of the etching solution for the copper molybdenum and alloy films as claimed in any one of claims 1 to 9, characterized in that hydrogen peroxide, a hydrogen peroxide stabilizer, an amine pH regulator, a complexing agent, a metal corrosion inhibitor and water are mixed to obtain the etching solution for the copper molybdenum and alloy films.
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| CN111663138A (en) * | 2020-07-08 | 2020-09-15 | 江苏和达电子科技有限公司 | Etching solution for copper-containing laminated film of liquid crystal panel and application thereof |
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