JPWO2010073887A1 - Photoresist stripper composition, photoresist stripping method and manufacturing method for laminated metal wiring board - Google Patents
Photoresist stripper composition, photoresist stripping method and manufacturing method for laminated metal wiring board Download PDFInfo
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- JPWO2010073887A1 JPWO2010073887A1 JP2010543992A JP2010543992A JPWO2010073887A1 JP WO2010073887 A1 JPWO2010073887 A1 JP WO2010073887A1 JP 2010543992 A JP2010543992 A JP 2010543992A JP 2010543992 A JP2010543992 A JP 2010543992A JP WO2010073887 A1 JPWO2010073887 A1 JP WO2010073887A1
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 111
- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 239000002184 metal Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 83
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052802 copper Inorganic materials 0.000 claims abstract description 77
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 51
- 239000000758 substrate Substances 0.000 claims abstract description 41
- 150000001413 amino acids Chemical class 0.000 claims abstract description 37
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011733 molybdenum Substances 0.000 claims abstract description 33
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 32
- 229910001182 Mo alloy Inorganic materials 0.000 claims abstract description 28
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004475 Arginine Substances 0.000 claims description 11
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 9
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004472 Lysine Substances 0.000 claims description 9
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 8
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 6
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 150000002337 glycosamines Chemical class 0.000 claims description 5
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 5
- 229930182474 N-glycoside Natural products 0.000 claims description 3
- 150000002341 glycosylamines Chemical class 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims 1
- 150000001408 amides Chemical group 0.000 abstract description 16
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 150000001565 benzotriazoles Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 45
- 229940024606 amino acid Drugs 0.000 description 29
- 235000001014 amino acid Nutrition 0.000 description 29
- 238000005260 corrosion Methods 0.000 description 27
- 230000007797 corrosion Effects 0.000 description 27
- 238000011156 evaluation Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 239000010953 base metal Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- -1 alkylbenzene sulfonate Chemical class 0.000 description 2
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 2
- 238000000861 blow drying Methods 0.000 description 2
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- DUFGYCAXVIUXIP-UHFFFAOYSA-N 4,6-dihydroxypyrimidine Chemical compound OC1=CC(O)=NC=N1 DUFGYCAXVIUXIP-UHFFFAOYSA-N 0.000 description 1
- PFJHUACESAVKDZ-GFCCVEGCSA-N 4-[(2r)-2-hydroxy-3-(propan-2-ylamino)propoxy]naphthalene-1,7-diol Chemical compound OC1=CC=C2C(OC[C@H](O)CNC(C)C)=CC=C(O)C2=C1 PFJHUACESAVKDZ-GFCCVEGCSA-N 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- AHLPHDHHMVZTML-UHFFFAOYSA-N Orn-delta-NH2 Natural products NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 description 1
- UTJLXEIPEHZYQJ-UHFFFAOYSA-N Ornithine Natural products OC(=O)C(C)CCCN UTJLXEIPEHZYQJ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 229960003624 creatine Drugs 0.000 description 1
- 239000006046 creatine Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
半導体基板やFPD基板の銅又は銅合金配線製造工程において使用する、ベンゾトリアゾール類やチオール基を有する化合物を含有せず、銅又は銅合金配線も銅又は銅合金とモリブデン又はモリブデン合金との積層金属配線も腐食しないフォトレジスト剥離剤組成物、それを使用した積層金属配線基板のフォトレジスト剥離方法及び製造方法である。本発明は、(A)2級アルカノールアミン及び/又は3級アルカノールアミンを1〜50重量%、(B)水溶性有機溶剤を5〜85重量%、(C)分子内にチオール基及びアミド構造をともに持たず、窒素原子を2個以上有するアミノ酸を0.002〜0.1重量%、(D)水を10〜93.998重量%含有し、(B)と(D)の合計量が49.9〜98.998重量%であり、水で重量比20倍に希釈した溶液のpHが8を超えるフォトレジスト剥離剤組成物である。It does not contain benzotriazoles or thiol group-containing compounds used in the copper or copper alloy wiring manufacturing process of semiconductor substrates and FPD substrates, and copper or copper alloy wiring is also a laminated metal of copper or copper alloy and molybdenum or molybdenum alloy A photoresist stripper composition that does not corrode wiring, and a photoresist stripping method and manufacturing method for a laminated metal wiring board using the same. The present invention comprises (A) secondary alkanolamine and / or tertiary alkanolamine in an amount of 1 to 50% by weight, (B) a water-soluble organic solvent in an amount of 5 to 85% by weight, and (C) a thiol group and an amide structure in the molecule. The amino acid having 2 or more nitrogen atoms and 0.002 to 0.1 wt% of the amino acid, (D) 10 to 93.998 wt% of water, and the total amount of (B) and (D) is This is a photoresist stripper composition having a pH of 49.9 to 98.998% by weight and having a pH of more than 8 in a solution diluted 20 times by weight with water.
Description
本発明はフォトレジスト剥離剤組成物に関し、詳細には、液晶ディスプレイに代表されるフラットパネルディプレイ(以下、FPDともいう。)基板や半導体基板の銅又は銅合金配線基板に好適に使用される、防食性及び剥離性に優れるフォトレジスト剥離剤組成物、並びにそれを用いた積層金属配線基板のフォトレジスト剥離方法及び積層金属配線基板の製造方法に関する。 The present invention relates to a photoresist remover composition, and in particular, is preferably used for a flat panel display (hereinafter also referred to as FPD) substrate represented by a liquid crystal display or a copper or copper alloy wiring substrate of a semiconductor substrate. The present invention relates to a photoresist remover composition excellent in corrosion resistance and peelability, a method for removing a photoresist from a laminated metal wiring board using the same, and a method for producing a laminated metal wiring board.
FPD基板や半導体基板は微細な配線を施した電極構造を有しており、その製造工程でフォトレジストが使用されている。例えば、基板上に形成されたアルミニウム、アルミニウム合金、銅、銅合金等の導電性金属層やSiO2膜等の絶縁膜上にフォトレジストを塗布し、これに露光、現像の処理を施してレジストパターンを形成し、このパターニングされたレジストをマスクとして上記導電性金属層や絶縁膜等をエッチングし、微細配線を形成した後、不要となったフォトレジスト層を剥離剤で除去して基板が製造される。An FPD substrate or a semiconductor substrate has an electrode structure with fine wiring, and a photoresist is used in the manufacturing process. For example, a photoresist is applied on a conductive metal layer such as aluminum, aluminum alloy, copper, or copper alloy formed on a substrate, or an insulating film such as SiO 2 film, and the resist is subjected to exposure and development. A pattern is formed, and the conductive metal layer, insulating film, and the like are etched using the patterned resist as a mask to form fine wiring, and then the unnecessary photoresist layer is removed with a release agent to produce a substrate. Is done.
従来、フォトレジスト剥離剤組成物としては、有機アルカリ、無機アルカリ、有機酸、無機酸、極性溶剤等の単一溶剤、またはこれらの混合溶液が用いられてきた。また、フォトレジスト剥離性を向上させるために、アミンと水との混合液を用いることもよく知られている。フォトレジスト剥離剤組成物には、微細配線を腐食しないことが求められる。配線材料としては、従来アルミニウムが多用されてきたため、アルミニウムに対する腐食抑止についてはさまざまな検討がなされてきた。 Conventionally, a single solvent such as an organic alkali, an inorganic alkali, an organic acid, an inorganic acid, a polar solvent, or a mixed solution thereof has been used as a photoresist stripping composition. It is also well known to use a mixed liquid of amine and water in order to improve photoresist peelability. The photoresist remover composition is required not to corrode fine wiring. Conventionally, aluminum has been widely used as a wiring material, and therefore various studies have been made on corrosion inhibition against aluminum.
しかし近年、基板の大型化や配線パターンの微細化に伴い、アルミニウムよりも抵抗率の低い銅又は銅合金を配線材料として用いることが試みられている。銅はアルカリ含有の溶液に腐食しやすい金属である上、アルミニウムと腐食溶解機構が異なり、アルミニウムで有効であった腐食抑止策はほとんど効果がない。そのため、銅又は銅合金に有効な防食剤が検討されている。例えば特許文献1には、−C(OH)=N−又は−CONH−なる原子団を含む五員ないし六員の複素環を有する複素環式化合物とアルカノールアミンとを含有する防食剤が半導体ウエハ上に形成された銅等の金属層を防食すると記載されている。 However, in recent years, attempts have been made to use copper or a copper alloy having a resistivity lower than that of aluminum as a wiring material in accordance with an increase in the size of a substrate and the miniaturization of a wiring pattern. Copper is a metal that is easily corroded by alkali-containing solutions, and the corrosion dissolution mechanism is different from that of aluminum. Corrosion suppression measures that were effective with aluminum are almost ineffective. Therefore, anticorrosives effective for copper or copper alloys have been studied. For example, Patent Document 1 discloses an anticorrosive containing a heterocyclic compound having a 5- or 6-membered heterocyclic ring containing an atomic group of —C (OH) ═N— or —CONH— and an alkanolamine as a semiconductor wafer. It describes that a metal layer such as copper formed thereon is anticorrosive.
特許文献2には、分子内にチオール基を有するアミノ酸又はその誘導体が銅配線等の金属腐食を防止すると記載されている。すなわち、分子内にチオール基を有するアミノ酸又はその誘導体が、良好な金属腐食防止作用を有し、銅配線の腐食や酸化を起こさないことが開示されている。この開示は、明らかに、分子内にチオール基を有していないアミノ酸を銅等の腐食防止剤において排除している。さらに、特許文献3には、銅とのキレート安定化定数が15以上であり、かつチオール基を有しないアミノ酸を含む銅配線用残渣洗浄液が開示されている。すなわち、チオール基を有していないグリシン、プロリン、ヒスチジン等がCuO溶解性に優れていることが開示されている。しかしながら、これらのアミノ酸の銅腐食量はリジンやアラニン等と同程度であることもまた開示されている。 Patent Document 2 describes that an amino acid having a thiol group in the molecule or a derivative thereof prevents metal corrosion such as copper wiring. That is, it is disclosed that an amino acid having a thiol group in the molecule or a derivative thereof has a good metal corrosion prevention action and does not cause corrosion or oxidation of copper wiring. This disclosure clearly excludes amino acids that do not have a thiol group in the molecule in corrosion inhibitors such as copper. Furthermore, Patent Document 3 discloses a copper wiring residue cleaning solution containing an amino acid having a chelate stabilization constant of 15 or more and having no thiol group. That is, it is disclosed that glycine, proline, histidine and the like not having a thiol group are excellent in CuO solubility. However, it is also disclosed that the copper corrosion amount of these amino acids is comparable to lysine, alanine and the like.
また、銅に対する強力な腐食抑止剤として、ベンゾトリアゾール類が知られている。 Further, benzotriazoles are known as strong corrosion inhibitors for copper.
しかし、従来の銅又は銅合金用の防食剤では防食性が必ずしも充分ではなかった。また、分子内にチオール基を有する化合物及びベンゾトリアゾール類は、銅又は銅合金の防食性は優れているものの、これらを含有するフォトレジスト剥離剤組成物で銅又は銅合金を含む基板を処理すると、銅又は銅合金表面に析出物が発生する。しかしながら、この析出物は通常の洗浄では除去できないため、別途、析出物除去処理が必要になるという問題があった。 However, conventional anticorrosives for copper or copper alloys have not always had sufficient anticorrosion properties. Moreover, although the compound and benzotriazole which have a thiol group in a molecule | numerator are excellent in the anticorrosive property of copper or a copper alloy, when the board | substrate containing copper or a copper alloy is processed with the photoresist stripping composition containing these, A precipitate is generated on the surface of copper or copper alloy. However, since this deposit cannot be removed by ordinary washing, there is a problem that a separate deposit removal treatment is required.
一方、銅又は銅合金はガラス等の下地基板との密着性が不充分である。そのため、密着性を向上させるために銅又は銅合金の配線の下地に別の金属層を積層することが必要である。このような下地金属層は補助膜とも称される。この下地金属層として一般的に検討されているのがモリブデン又はモリブデン合金である。 On the other hand, copper or a copper alloy has insufficient adhesion to a base substrate such as glass. Therefore, in order to improve the adhesion, it is necessary to laminate another metal layer on the base of the copper or copper alloy wiring. Such a base metal layer is also called an auxiliary film. As the base metal layer, molybdenum or a molybdenum alloy is generally considered.
モリブデン又はモリブデン合金自身は防食性に優れた金属であり、単独ではフォトレジスト剥離剤組成物で処理しても腐食することはほとんどない。しかし、銅又は銅合金とモリブデン又はモリブデン合金が接触した状態では、電池効果によりモリブデン又はモリブデン合金の腐食が大幅に加速されるという現象が確認されている。これに対して従来の銅又は銅合金用防食剤では、銅又は銅合金を防食できたとしても、銅又は銅合金と接触したモリブデン又はモリブデン合金の腐食を抑制することはできなかった。すなわち、基板上にモリブデン又はモリブデン合金の下地金属層を形成し、さらにその上に銅又は銅合金層を形成し、パターニングされたフォトレジストを介して下地金属層と銅又は銅合金層を一括又は逐次エッチングした後、不要となったフォトレジストをフォトレジスト剥離剤組成物を使用して剥離除去しようとすると、配線パターン化されたモリブデン又はモリブデン合金の下地金属層上の銅又は銅合金配線において、下地金属層のほうが銅又は銅合金配線よりも多く腐食してしまうか、又は、場合によっては、銅又は銅合金配線のほうがより腐食してしまい、積層金属配線が形成されないという問題が生じる。 Molybdenum or molybdenum alloy itself is a metal with excellent anticorrosion properties, and by itself, it hardly corrodes even when treated with a photoresist stripper composition. However, it has been confirmed that in the state where copper or copper alloy and molybdenum or molybdenum alloy are in contact, corrosion of molybdenum or molybdenum alloy is greatly accelerated by the battery effect. On the other hand, with the conventional anticorrosive agent for copper or copper alloy, even if copper or copper alloy could be anticorrosive, corrosion of molybdenum or molybdenum alloy in contact with copper or copper alloy could not be suppressed. That is, a base metal layer of molybdenum or a molybdenum alloy is formed on a substrate, a copper or copper alloy layer is further formed thereon, and the base metal layer and the copper or copper alloy layer are collectively or via a patterned photoresist. After sequential etching, when the photoresist that is no longer needed is peeled off using the photoresist stripper composition, in the copper or copper alloy wiring on the underlying metal layer of the wiring patterned molybdenum or molybdenum alloy, The base metal layer is more corroded than the copper or copper alloy wiring, or in some cases, the copper or copper alloy wiring is more corroded, resulting in a problem that the laminated metal wiring is not formed.
本発明は、半導体基板及びFPD基板の銅又は銅合金配線製造工程において、ベンゾトリアゾール類およびチオール基を有する化合物を含有せず、基板上に形成された銅又は銅合金配線及び銅又は銅合金とモリブデン又はモリブデン合金との積層金属配線を腐食させることなくフォトレジストを剥離することができるフォトレジスト剥離剤組成物、それを使用した積層金属配線基板のフォトレジスト剥離方法及び積層金属配線基板の製造方法を提供することを目的とする。 In the copper or copper alloy wiring manufacturing process of the semiconductor substrate and the FPD substrate, the present invention does not contain benzotriazoles and a compound having a thiol group, and the copper or copper alloy wiring and the copper or copper alloy formed on the substrate Photoresist stripper composition capable of stripping photoresist without corroding multilayer metal wiring with molybdenum or molybdenum alloy, photoresist stripping method for multilayer metal wiring board using the same, and method for manufacturing multilayer metal wiring board The purpose is to provide.
本発明者は鋭意検討を行った結果、2級及び/又は3級アルカノールアミン並びに水溶性有機溶剤とともに分子内にチオール基を有せず、窒素原子を2個以上有するアミノ酸を含有するフォトレジスト剥離剤組成物が、銅又は銅合金配線に対しても、銅又は銅合金とモリブデン又はモリブデン合金との積層金属配線に対しても、優れた防食性を有するとともに、フォトレジスト剥離性能も良好であることを見出し、本発明を完成させた。 As a result of intensive studies, the present inventor removed a photoresist containing a secondary and / or tertiary alkanolamine and a water-soluble organic solvent and an amino acid having no thiol group in the molecule and having two or more nitrogen atoms. The agent composition has excellent anticorrosion properties for copper or copper alloy wiring and laminated metal wiring of copper or copper alloy and molybdenum or molybdenum alloy, and also has good photoresist stripping performance. As a result, the present invention has been completed.
すなわち、本発明は(A)2級アルカノールアミン及び/又は3級アルカノールアミン並びに(B)水溶性有機溶剤を含有するとともに、さらに(C)分子内にチオール基及びアミド構造をともに持たず、窒素原子を2個以上有するアミノ酸を0.002〜0.1重量%含有し、水で重量比20倍に希釈した溶液のpHが8を超えることを特徴とするフォトレジスト剥離剤組成物である。
本発明のフォトレジスト剥離剤組成物の1態様においては、(A)2級アルカノールアミン及び/又は3級アルカノールアミンを1〜50重量%、(B)水溶性有機溶剤を49.9〜98.998重量%、(C)分子内にチオール基及びアミド構造をともに持たず、窒素原子を2個以上有するアミノ酸を0.002〜0.1重量%含有する。
本発明のフォトレジスト剥離剤組成物の他の態様においては、さらに(D)水を含有する。この場合において、本発明のフォトレジスト剥離剤組成物の他の1態様においては、水(D)を水溶性有機溶剤(B)の一部分に代えて含有することができる。すなわち、(A)2級アルカノールアミン及び/又は3級アルカノールアミンを1〜50重量%、(B)水溶性有機溶剤を5〜85重量%、(C)分子内にチオール基及びアミド構造をともに持たず、窒素原子を2個以上有するアミノ酸を0.002〜0.1重量%、(D)水を10〜93.998重量%含有し、(B)と(D)の合計量が49.9〜98.998重量%である。
本発明のフォトレジスト剥離剤組成物の1態様においては、アミノ酸(C)が、アルギニン、グリコシアミン、ヒスチジン及びリジンからなる群から選択される少なくとも1種である。
また、本発明のフォトレジスト剥離剤組成物の他の1態様においては、アミノ酸(C)が、アルギニン、グリコシアミン及びリジンからなる群から選択される少なくとも1種である。
本発明のフォトレジスト剥離剤組成物の他の1態様においては、また、アミノ酸(C)が、アルギニンであってよい。
本発明のフォトレジスト剥離剤組成物においては、2級アルカノールアミン及び/又は3級アルカノールアミン(A)が、ジエタノールアミン、N−メチルエタノールアミン、N−メチルジエタノールアミン及びトリエタノールアミンからなる群から選択される少なくとも1種である。
本発明はまた、フォトレジストを使用して1層又は複数層のモリブデン若しくはモリブデン合金層と1層又は複数層の銅若しくは銅合金層との積層金属配線を基板上に形成する際に、不要となったフォトレジストを本発明のフォトレジスト剥離剤組成物を使用して剥離除去することを特徴とするモリブデン又はモリブデン合金層と銅又は銅合金層との積層金属配線基板のフォトレジスト剥離方法でもある。
本発明はさらにまた、基板上に1層又は複数層のモリブデン若しくはモリブデン合金層と1層又は複数層の銅若しくは銅合金層とを積層し、つぎに、パターニングされたフォトレジストを介して前記積層された金属層をエッチングした後、不要となったフォトレジストを本発明のフォトレジスト剥離剤組成物を使用して剥離除去することを特徴とする積層金属配線基板の製造方法でもある。
以下、これらの本発明をとくに区別することなく単に「本発明」ともいう。That is, the present invention contains (A) a secondary alkanolamine and / or tertiary alkanolamine and (B) a water-soluble organic solvent, and (C) has neither a thiol group nor an amide structure in the molecule, and nitrogen. A photoresist stripping composition comprising a solution containing 0.002 to 0.1% by weight of an amino acid having 2 or more atoms and diluted to 20 times by weight with water and having a pH exceeding 8.
In one embodiment of the photoresist stripping composition of the present invention, (A) secondary alkanolamine and / or tertiary alkanolamine is 1 to 50 wt%, and (B) water-soluble organic solvent is 49.9 to 98. 998% by weight, (C) 0.002 to 0.1% by weight of an amino acid having neither a thiol group nor an amide structure in the molecule and having two or more nitrogen atoms.
In another aspect of the photoresist remover composition of the present invention, (D) water is further contained. In this case, in another embodiment of the photoresist stripping composition of the present invention, water (D) can be contained instead of a part of the water-soluble organic solvent (B). That is, (A) secondary alkanolamine and / or tertiary alkanolamine is 1 to 50% by weight, (B) water-soluble organic solvent is 5 to 85% by weight, (C) both thiol group and amide structure in the molecule It contains 0.002 to 0.1% by weight of an amino acid having 2 or more nitrogen atoms, (D) 10 to 93.998% by weight of water, and the total amount of (B) and (D) is 49. 9 to 98.998% by weight.
In one embodiment of the photoresist stripping composition of the present invention, the amino acid (C) is at least one selected from the group consisting of arginine, glycosamine, histidine and lysine.
In another aspect of the photoresist stripping composition of the present invention, the amino acid (C) is at least one selected from the group consisting of arginine, glycosylamine and lysine.
In another embodiment of the photoresist stripper composition of the present invention, the amino acid (C) may also be arginine.
In the photoresist stripping composition of the present invention, the secondary alkanolamine and / or tertiary alkanolamine (A) is selected from the group consisting of diethanolamine, N-methylethanolamine, N-methyldiethanolamine and triethanolamine. At least one kind.
The present invention also eliminates the need for using a photoresist to form a laminated metal wiring of one or more layers of molybdenum or molybdenum alloy layers and one or more layers of copper or copper alloy layers on a substrate. It is also a photoresist stripping method for a multilayer metal wiring board of a molybdenum or molybdenum alloy layer and a copper or copper alloy layer, characterized in that the stripped photoresist is stripped and removed using the photoresist stripping composition of the present invention. .
The present invention further provides a method of laminating one or more molybdenum or molybdenum alloy layers and one or more copper or copper alloy layers on a substrate, and then laminating the laminate via a patterned photoresist. After the etched metal layer is etched, the photoresist that is no longer needed is stripped and removed using the photoresist stripper composition of the present invention.
Hereinafter, the present invention is also simply referred to as “the present invention” without particular distinction.
本発明は、上述の構成により、
(1)半導体基板およびFPD基板の金属配線製造工程において、フォトレジストに対する優れた剥離性を有する。
(2)銅又は銅合金配線、及び、銅又は銅合金とモリブデン又はモリブデン合金の積層金属配線のいずれに対しても、優れた防食性を有する。
(3)本発明のフォトレジスト剥離剤組成物を使用すると、配線パターン化されたモリブデン又はモリブデン合金の下地金属層上の銅又は銅合金配線において、下地金属層や銅又は銅合金配線の腐食を防止することにより、下地層の過度の腐食によるアンダーカット形状や銅又は銅合金層の腐食による配線幅のやせ細り等のない良好な積層金属配線を形成することができる。The present invention has the above configuration.
(1) In the metal wiring manufacturing process of a semiconductor substrate and an FPD substrate, it has excellent releasability from a photoresist.
(2) It has excellent anticorrosive properties for any of copper or copper alloy wiring and laminated metal wiring of copper or copper alloy and molybdenum or molybdenum alloy.
(3) When the photoresist stripping composition of the present invention is used, the copper or copper alloy wiring on the wiring-patterned molybdenum or molybdenum alloy base metal layer corrodes the base metal layer or copper or copper alloy wiring. By preventing this, it is possible to form a favorable laminated metal wiring that does not have an undercut shape due to excessive corrosion of the underlayer or a thinning of the wiring width due to corrosion of the copper or copper alloy layer.
本発明において、(A)2級アルカノールアミン及び/又は3級アルカノールアミン(本明細書中、単に「アルカノールアミン(A)」ともいう。)としては、2級アルカノールアミンのみであってもよく、3級アルカノールアミンのみであってもよく、2級アルカノールアミン及び3級アルカノールアミンであってもよい。アルカノールアミン(A)としては特に限定されず、2級アルカノールアミンとしては、例えば、ジエタノールアミン、N−メチルエタノールアミン、N−エチルエタノールアミン等を挙げることができ、3級アルカノールアミンとしては、例えば、N−メチルジエタノールアミン、N−エチルジエタノールアミン、N,N−ジメチルエタノールアミン、N,N−ジエチルエタノールアミン、トリエタノールアミン等が挙げられる。これらは1種のみ用いてもよく、2種以上を同時に用いてもよい。この中でも入手の容易さ及び剥離性と銅又は銅合金に対する防食性の兼備の点から、ジエタノールアミン、N−メチルエタノールアミン、N−メチルジエタノールアミン、トリエタノールアミン、これらの任意の組み合わせが好ましい。 In the present invention, (A) secondary alkanolamine and / or tertiary alkanolamine (also referred to herein as simply “alkanolamine (A)”) may be only secondary alkanolamine, Only a tertiary alkanolamine may be sufficient, and a secondary alkanolamine and a tertiary alkanolamine may be sufficient. The alkanolamine (A) is not particularly limited, and examples of the secondary alkanolamine include diethanolamine, N-methylethanolamine, and N-ethylethanolamine. Examples of the tertiary alkanolamine include: N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethanolamine and the like can be mentioned. These may be used alone or in combination of two or more. Among these, diethanolamine, N-methylethanolamine, N-methyldiethanolamine, triethanolamine, and any combination thereof are preferable from the viewpoints of easy availability, releasability, and anticorrosive properties for copper or a copper alloy.
アルカノールアミン(A)の添加量は、剥離剤組成物中の1〜50重量%であることが好ましい。この範囲内であると剥離性が充分良好であり、低粘度で取扱いが良好である。より好ましくは3〜45重量%である。 The amount of alkanolamine (A) added is preferably 1 to 50% by weight in the release agent composition. Within this range, the peelability is sufficiently good, and the viscosity is low and the handling is good. More preferably, it is 3 to 45% by weight.
本発明において、水溶性有機溶剤(B)としては特に限定されず、例えば、アセトン、メタノール、エタノール、ジエチレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールジメチルエーテル、プロピレングリコールメチルエーテル、ジプロピレングリコール、N−メチル−2−ピロリドン、N,N−ジメチルアセトアミド、N,N−ジメチルホルムアミド、アセトニトリル、ジメチルスルホキシド、スルホラン、エチレンカーボネート等が挙げられる。これらは1種のみ用いてもよく、2種以上を同時に用いてもよい。この中でもジエチレングリコールモノブチルエーテル、N,N−ジメチルアセトアミド、ジエチレングリコールが好適である。 In the present invention, the water-soluble organic solvent (B) is not particularly limited. For example, acetone, methanol, ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether, diethylene glycol, Examples include propylene glycol, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, acetonitrile, dimethyl sulfoxide, sulfolane, and ethylene carbonate. These may be used alone or in combination of two or more. Of these, diethylene glycol monobutyl ether, N, N-dimethylacetamide, and diethylene glycol are preferred.
水溶性有機溶剤(B)の添加量は、剥離剤組成物中の49.9〜98.998重量%であることが好ましい。この範囲内であるとフォトレジストの剥離性と銅又は銅合金防食性とが充分良好に発揮される。より好ましくは54.998〜96.998重量%である。 The amount of the water-soluble organic solvent (B) added is preferably 49.9 to 98.998% by weight in the release agent composition. Within this range, the peelability of the photoresist and the corrosion resistance of copper or copper alloy are sufficiently satisfactorily exhibited. More preferably, it is 54.998-96.998 weight%.
本発明において、アミノ酸(C)は、分子内にチオール基及びアミド構造をともに持たず、窒素原子を2個以上有する。このようなアミノ酸は、窒素原子を1個のみ含有する一般的なアミノ酸と比較して、金属に対する配位点が多く、防食効果が高いと考えられる。また、水酸基を有するアミノ酸と比較すると、窒素原子は水酸基より銅に対する配位力が強いため、高い防食効果を示すと考えられる。一方、チオール基を有するアミノ酸と比較すると、窒素原子はチオール基より銅に対する配位力が弱いため、銅の表面に析出することもなく、適当な防食性を示すと考えられる。また、窒素原子を2個以上有していてもアミド構造を有するものは防食性に劣る。 In the present invention, amino acid (C) has neither a thiol group nor an amide structure in the molecule, and has two or more nitrogen atoms. Such an amino acid has many coordination points with respect to a metal compared with a general amino acid containing only one nitrogen atom, and is considered to have a high anticorrosion effect. In addition, compared with amino acids having a hydroxyl group, the nitrogen atom has a higher coordinating power to copper than the hydroxyl group, and thus is considered to exhibit a high anticorrosive effect. On the other hand, compared with an amino acid having a thiol group, the nitrogen atom has a lower coordination power to copper than the thiol group, so it is considered that the nitrogen atom does not precipitate on the surface of copper and exhibits an appropriate anticorrosive property. Moreover, even if it has two or more nitrogen atoms, those having an amide structure are inferior in corrosion resistance.
アミノ酸(C)としては、分子内にチオール基及びアミド構造をともに持たず、窒素原子を2個以上、好ましくは2〜4個、有するものであり、例えば、ヒスチジン、アルギニン、リジン、グリコシアミン、クレアチン、オルニチン等を挙げることができる。これらは1種のみ使用してもよく又は2種以上使用してもよい。また、例えば、アルギニン、グリコシアミン、ヒスチジン及びリジンからなる群から選択される少なくとも1種であってもよく、アルギニン、グリコシアミン及びリジンからなる群から選択される少なくとも1種であってもよく、又は、アルギニンであってもよい。これらのうち、入手の容易さ及び防食性の観点からヒスチジン、アルギニン、リジン、グリコシアミンが好ましい。 The amino acid (C) does not have both a thiol group and an amide structure in the molecule and has 2 or more, preferably 2 to 4, nitrogen atoms. For example, histidine, arginine, lysine, glycosamine, creatine Ornithine and the like. These may be used alone or in combination of two or more. Further, for example, it may be at least one selected from the group consisting of arginine, glycosamine, histidine and lysine, may be at least one selected from the group consisting of arginine, glycosamine and lysine, or Arginine may be used. Of these, histidine, arginine, lysine, and glycosylamine are preferable from the viewpoint of availability and anticorrosion.
アミノ酸(C)の含有量は、剥離剤組成中の0.002〜0.1重量%である。この範囲内であると、銅又は銅合金及びモリブデン又はモリブデン合金に対する防食性が充分であり、この範囲を超えると、フォトレジストの剥離性が低下するほか、アミノ酸(C)をまったく含有しない場合よりもかえって銅又は銅合金に対する防食性を低下させる場合があるため不適である。好ましくは、0.003〜0.1重量%であり、より好ましくは0.005〜0.1重量%である。 The content of the amino acid (C) is 0.002 to 0.1% by weight in the release agent composition. If it is within this range, the corrosion resistance to copper or copper alloy and molybdenum or molybdenum alloy is sufficient, and if it exceeds this range, the peelability of the photoresist is lowered and more than the case where no amino acid (C) is contained. On the contrary, it is not suitable because it may reduce the corrosion resistance of copper or copper alloy. Preferably, it is 0.003-0.1 weight%, More preferably, it is 0.005-0.1 weight%.
本発明においては、上記アルカノールアミン(A)、水溶性有機溶剤(B)及びアミノ酸(C)の合計が組成物中の100重量%を占めることができる。 In the present invention, the total of the alkanolamine (A), the water-soluble organic solvent (B) and the amino acid (C) can occupy 100% by weight in the composition.
本発明のフォトレジスト剥離剤組成物の他の態様においては、さらに(D)水を含有する。この場合において、本発明のフォトレジスト剥離剤組成物の他の1態様においては、水溶性有機溶剤(B)の一部分に代えて(D)水を含有することができる。この場合、水溶性有機溶剤(B)を好ましくは5〜85重量%、より好ましくは10〜75重量%、水(D)を好ましくは10〜93.998重量%、より好ましくは10〜85重量%、さらに好ましくは15〜80重量%含有し、(B)と(D)の合計量が好ましくは49.9〜98.998重量%、より好ましくは54.998〜96.998重量%である。水(D)を配合することにより、フォトレジストの剥離性を一層向上させるとともに、アルカノールアミン(A)と水溶性有機溶剤(B)が引火点を有する場合でも、剥離剤組成物としての引火点をなくす効果がある。水(D)を配合する場合、上記範囲内であると、フォトレジストの剥離性向上効果が得られ、また引火点をなくす効果を得られる。上記範囲を超えると、他成分の濃度が低下することにより、フォトレジストの剥離性が低下する場合がある。 In another aspect of the photoresist remover composition of the present invention, (D) water is further contained. In this case, in another embodiment of the photoresist stripping composition of the present invention, (D) water can be contained instead of a part of the water-soluble organic solvent (B). In this case, the water-soluble organic solvent (B) is preferably 5 to 85% by weight, more preferably 10 to 75% by weight, and the water (D) is preferably 10 to 93.998% by weight, more preferably 10 to 85% by weight. %, More preferably 15 to 80% by weight, and the total amount of (B) and (D) is preferably 49.9 to 98.998% by weight, more preferably 54.998 to 96.998% by weight. . By blending water (D), the releasability of the photoresist is further improved, and even when the alkanolamine (A) and the water-soluble organic solvent (B) have a flash point, the flash point as a release agent composition. There is an effect to eliminate. When blending water (D), if it is within the above range, the effect of improving the peelability of the photoresist can be obtained, and the effect of eliminating the flash point can be obtained. When the above range is exceeded, the concentration of other components may decrease, and the peelability of the photoresist may decrease.
本発明におけるフォトレジスト剥離剤組成物は、アルカノールアミン(A)を含有しており、水溶液はアルカリ性を有している。フォトレジスト剥離剤組成物が酸性および中性を有している場合、フォトレジストの剥離性が不充分となる場合がある。充分なフォトレジストの剥離性を得るのに必要なアルカリ性の指標としては、フォトレジスト剥離剤組成物を水で重量比20倍に希釈した場合に、希釈溶液のpHが8を超えることである。好ましくはpHが9以上である。温度によりpHの値が変動する場合は25℃における値である。 The photoresist remover composition in the present invention contains alkanolamine (A), and the aqueous solution has alkalinity. When the photoresist stripping composition has acidity and neutrality, the stripping property of the photoresist may be insufficient. An alkaline index necessary for obtaining sufficient photoresist peelability is that the pH of the diluted solution exceeds 8 when the photoresist remover composition is diluted 20 times by weight with water. The pH is preferably 9 or more. When the pH value varies depending on the temperature, the value is at 25 ° C.
本発明のフォトレジスト剥離剤組成物は、上記成分の他に、本発明の目的を阻害しない範囲で界面活性剤(例えば、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル)、消泡剤(例えば、シリコーンオイル)等の添加剤を含有することができる。上記添加剤の含有量は、その種類によるので一概に定めないが、例えば、0.001〜5重量%が好ましく、より好ましくは0.01〜1重量%である。 In addition to the above components, the photoresist stripper composition of the present invention has a surfactant (for example, alkylbenzene sulfonate, polyoxyethylene alkyl ether), an antifoaming agent (for example, for example) as long as the object of the present invention is not impaired. An additive such as silicone oil) can be contained. Since the content of the additive depends on the type of the additive, it is not generally determined. For example, 0.001 to 5% by weight is preferable, and 0.01 to 1% by weight is more preferable.
本発明のフォトレジスト剥離剤組成物は、上記各成分の所要量を常法により混合することで調製することができる。 The photoresist remover composition of the present invention can be prepared by mixing the required amounts of the above components by a conventional method.
本発明のフォトレジスト剥離剤組成物は、半導体基板およびFPD基板の製造工程において、金属配線等のエッチング処理後に不要となったフォトレジストを剥離するために用いられる。上記金属配線としては特に限定されず、当該技術分野で使用される金属配線に適用することができるが、なかでも、モリブデン又はモリブデン合金層と銅又は銅合金層との積層金属配線に好適に使用することができる。本発明のフォトレジスト剥離剤組成物は常温(25℃)のほか、例えば30℃〜80℃に加熱して使用することができる。剥離に要する時間は、フォトレジストの変質度合い等によるが、一般には、例えば30秒〜10分間程度である。処理後、必要に応じて水洗、空気ブロー乾燥等を行うことができる。上記フォトレジストとしては特に限定されず、当該技術分野で使用される感光性樹脂(例えば、ポジ型フォトレジスト(ノボラック樹脂、ナフトキノンジアジド系感光剤及び溶剤を主成分とするポジ型フォトレジスト)等)を使用することができる。 The photoresist stripping composition of the present invention is used for stripping a photoresist that is no longer necessary after an etching process for metal wiring or the like in the manufacturing process of a semiconductor substrate and an FPD substrate. The metal wiring is not particularly limited and can be applied to metal wiring used in the technical field, but among them, it is preferably used for laminated metal wiring of molybdenum or molybdenum alloy layer and copper or copper alloy layer. can do. The photoresist remover composition of the present invention can be used by heating to, for example, 30 ° C. to 80 ° C. in addition to normal temperature (25 ° C.). The time required for stripping depends on the degree of alteration of the photoresist, but is generally about 30 seconds to 10 minutes, for example. After the treatment, washing with water, air blow drying and the like can be performed as necessary. The photoresist is not particularly limited and is a photosensitive resin used in the technical field (for example, a positive photoresist (a novolak resin, a naphthoquinonediazide-based photosensitive agent and a positive photoresist mainly composed of a solvent), etc.) Can be used.
具体的には、本発明のフォトレジスト剥離剤組成物を用いる積層金属配線基板のフォトレジスト剥離方法は、フォトレジストを使用して1層又は複数層のモリブデン若しくはモリブデン合金層と1層又は複数層の銅若しくは銅合金層との積層金属配線を基板上に形成する際に、不要となったフォトレジストを本発明のフォトレジスト剥離剤組成物を使用して剥離除去する。こうすることにより、モリブデン又はモリブデン合金層と銅又は銅合金層との積層金属配線において、下地金属層が過度に腐食してアンダーカット形状をなすことや、逆に、銅又は銅合金層が過度に腐食して銅又は銅合金配線の線幅がやせる等のことが抑制され、エッチングで形成された配線断面形状を損なうことなく、良好なモリブデン又はモリブデン合金層と銅又は銅合金層との積層金属配線が形成される。なお、積層金属配線の態様としては、例えば、基板上から順に、モリブデン又はモリブデン合金/銅又は銅合金/モリブデン又はモリブデン合金の3層積層金属配線、モリブデン又はモリブデン合金/銅又は銅合金の2層積層金属配線等があり得る。 Specifically, the photoresist stripping method of the laminated metal wiring board using the photoresist stripping composition of the present invention uses one or more molybdenum or molybdenum alloy layers and one or more layers using a photoresist. When the laminated metal wiring with the copper or copper alloy layer is formed on the substrate, the unnecessary photoresist is peeled off using the photoresist stripper composition of the present invention. By doing so, in the laminated metal wiring of the molybdenum or molybdenum alloy layer and the copper or copper alloy layer, the base metal layer is excessively corroded to form an undercut shape, and conversely, the copper or copper alloy layer is excessively excessive. A good lamination of molybdenum or a molybdenum alloy layer and a copper or copper alloy layer without damaging the wire width of the copper or copper alloy wiring due to corrosion and without damaging the wiring cross-sectional shape formed by etching. Metal wiring is formed. As an aspect of the laminated metal wiring, for example, in order from the substrate, a three-layer laminated metal wiring of molybdenum or molybdenum alloy / copper or copper alloy / molybdenum or molybdenum alloy, or two layers of molybdenum or molybdenum alloy / copper or copper alloy. There may be laminated metal wiring or the like.
また、本発明のフォトレジスト剥離剤組成物を用いる積層金属配線基板の製造方法は、基板上に1層又は複数層のモリブデン若しくはモリブデン合金層と1層又は複数層の銅若しくは銅合金層とを積層し、つぎに、パターニングされたフォトレジストを介して積層された金属層をエッチングした後、不要となったフォトレジストを本発明のフォトレジスト剥離剤組成物を使用して剥離除去する。この際、エッチング処理としては、積層金属層を一括エッチングしてもよく、又は、各積層を逐次にエッチングしてもよい。上記エッチング処理方法としては特に限定されず、当該技術分野で使用される方法(例えば、エッチング液を用いる方法、ドライエッチング方法等。)を適用することができる。剥離除去の後、必要に応じて水洗、空気ブロー乾燥等を行い、基板を得ることができる。 Moreover, the manufacturing method of the laminated metal wiring board using the photoresist remover composition of the present invention comprises a single layer or a plurality of layers of molybdenum or a molybdenum alloy layer and a single layer or a plurality of layers of copper or a copper alloy layer on the substrate. After laminating and then etching the laminated metal layer through the patterned photoresist, the photoresist that is no longer needed is stripped and removed using the photoresist stripper composition of the present invention. At this time, as the etching process, the stacked metal layers may be etched at once, or each stacked layer may be etched sequentially. The etching method is not particularly limited, and a method used in the technical field (for example, a method using an etching solution, a dry etching method, or the like) can be applied. After peeling and removing, washing with water, air blow drying and the like can be performed as necessary to obtain a substrate.
以下に実施例によって本発明をより具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
実施例1〜17、比較例1〜21
表1及び表2の配合によりそれぞれ各成分を混合し、フォトレジスト剥離剤組成物を得た。なお、表中の略号は次のとおりである。
MDEA:N−メチルジエタノールアミン
DEA:N,N−ジエタノールアミン
MEA:モノエタノールアミン
TEA:トリエタノールアミン
MMEA:N−メチルエタノールアミン
DMAC:N,N−ジメチルアセトアミド
BDG:ジエチレングリコールモノブチルエーテル
4,6−DHP:4,6−ジヒドロキシピリミジンExamples 1-17, Comparative Examples 1-21
Each component was mixed by the mixing | blending of Table 1 and Table 2, respectively, and the photoresist peeling agent composition was obtained. The abbreviations in the table are as follows.
MDEA: N-methyldiethanolamine DEA: N, N-diethanolamine MEA: monoethanolamine TEA: triethanolamine MMEA: N-methylethanolamine DMAC: N, N-dimethylacetamide BDG: diethylene glycol monobutyl ether 4, 6-DHP: 4 , 6-Dihydroxypyrimidine
評価1:銅単膜防食性
ガラス上に50nm厚の銅膜をスパッタリングにより成膜した基板を評価対象物とした。50℃に調整したフォトレジスト剥離剤組成物に基板を浸漬し、通常の処理時間は10分以下程度であるところ、その3倍の30分間処理をした。浸漬処理後、基板を水洗および空気ブロー乾燥した。基板の銅膜の残り具合を目視にて観察した。
判定基準
(合格)
○:変化なし
(以下、不合格)
△:一部、銅膜の消失あり
×:銅膜がほぼ消失Evaluation 1: Copper single-film anticorrosive property A substrate on which a copper film having a thickness of 50 nm was formed on glass by sputtering was used as an evaluation object. The substrate was dipped in a photoresist remover composition adjusted to 50 ° C., and the treatment time was about 10 minutes or less, but the treatment was performed for 3 times that of 30 minutes. After the immersion treatment, the substrate was washed with water and air-dried. The remaining state of the copper film on the substrate was visually observed.
Judgment criteria
(Pass)
○: No change
(Failure)
Δ: Some copper film disappeared ×: Copper film almost disappeared
評価2:銅/モリブデン積層配線防食性(Cu/Mo配線防食性)
ガラス上にモリブデン、銅の順にスパッタリングで成膜した上に、フォトレジスト(ノボラック樹脂、ナフトキノンジアジド系感光剤及び溶剤を主成分とするポジ型フォトレジスト)を成膜し、UV露光及び現像によりフォトレジストのパターニングを行った後、過酸化水素含有の銅エッチャントにて40℃/50秒間の条件で銅およびモリブデンを一括エッチングした基板を評価対象とした。40℃に調整したフォトレジスト剥離剤組成物に基板を浸漬し、10分間処理をした。浸漬処理後、基板を水洗および空気ブロー乾燥した。電子顕微鏡を用いて基板を観察し、銅およびモリブデンの腐食具合を確認した。判定は銅(Cu)、モリブデン(Mo)別々に行った。
判定基準
(合格)
○:腐食なし
(以下、不合格)
△:僅かに腐食あり
×:大幅に腐食ありEvaluation 2: Corrosion resistance of copper / molybdenum multilayer wiring (Cu / Mo wiring corrosion resistance)
Films of molybdenum and copper are sputtered onto glass in this order, and then a photoresist (a novolak resin, a positive photoresist mainly composed of a naphthoquinone diazide-based photosensitizer and a solvent) is formed, and a photo is formed by UV exposure and development. After patterning the resist, a substrate on which copper and molybdenum were collectively etched with a copper etchant containing hydrogen peroxide under the condition of 40 ° C./50 seconds was used as an evaluation target. The substrate was immersed in a photoresist remover composition adjusted to 40 ° C. and treated for 10 minutes. After the immersion treatment, the substrate was washed with water and air-dried. The board | substrate was observed using the electron microscope and the corrosion condition of copper and molybdenum was confirmed. The determination was made separately for copper (Cu) and molybdenum (Mo).
Judgment criteria
(Pass)
○: No corrosion
(Failure)
△: Slightly corrosive ×: Significantly corroded
評価3:フォトレジスト剥離性
ガラス基板上にSiN膜をCVDで成膜した上に、フォトレジストを成膜し、UV露光および現像によりフォトレジストのパターニングを行った後、フッ素系のガスにてSiNをドライエッチングした基板を評価対象とした。40℃に調整したフォトレジスト剥離剤組成物に基板を浸漬し、30秒間処理をした。浸漬処理後、基板を水洗および空気ブロー乾燥した。電子顕微鏡を用いて基板を観察し、フォトレジストの剥離具合を確認した。
判定基準
(合格)
○:剥離残りなし
(以下、不合格)
△:僅かに剥離残りあり
×:ほとんど剥離できずEvaluation 3: Photoresist releasability A SiN film is formed on a glass substrate by CVD, a photoresist is formed, the photoresist is patterned by UV exposure and development, and then SiN is used with a fluorine-based gas. The substrate subjected to dry etching was evaluated. The substrate was immersed in a photoresist remover composition adjusted to 40 ° C. and treated for 30 seconds. After the immersion treatment, the substrate was washed with water and air-dried. The substrate was observed using an electron microscope to confirm the peeling of the photoresist.
Judgment criteria (pass)
○: No peeling residue
(Failure)
Δ: Slightly remaining peeling ×: Almost no peeling
各フォトレジスト剥離剤組成物について、まず評価1を行い、判定が「○」又は「△」のものについて、評価2を行った。評価2において判定がすべて「○」であったものについて、評価3を行った。ただし、比較例14、15については評価1、2の結果に関わらず評価3を行った。評価結果は表1、表2に記載した。また、各フォトレジスト剥離剤組成物について水で重量比20倍希釈した水溶液を作成し、pHメーターを用いて25℃におけるpHを測定した。 For each photoresist stripping composition, first, evaluation 1 was performed, and evaluation 2 was performed for those having a determination of “◯” or “Δ”. Evaluation 3 was performed for all the evaluations in evaluation 2 that were “◯”. However, for Comparative Examples 14 and 15, Evaluation 3 was performed regardless of the results of Evaluations 1 and 2. The evaluation results are shown in Tables 1 and 2. Moreover, the aqueous solution diluted 20 times weight ratio with water about each photoresist remover composition was created, and pH at 25 degreeC was measured using the pH meter.
評価の結果、1級アルカノールアミンを含有するフォトレジスト剥離剤組成物(比較例1、3)、分子内にチオール基及びアミド構造を有せず、窒素原子を2個以上有するアミノ酸を含有するが、1級アルカノールアミンを含有するフォトレジスト剥離剤組成物(比較例10)、分子内にチオール基及びアミド構造を有せず、窒素原子を2個以上有するアミノ酸を0.1重量%を大幅に超えて含有するフォトレジスト剥離剤組成物(比較例4、6、18〜20)、2級アルカノールアミンと水溶性有機溶剤を含有するが、分子内にチオール基及びアミド構造を有せず、窒素原子を2個以上有するアミノ酸を含有しないフォトレジスト剥離剤組成物(比較例17)、3級アルカノールアミンと、分子内にチオール基及びアミド構造を有せず、窒素原子を2個以上有するアルカノールアミンを含有するが、水溶性有機溶剤を含有しないフォトレジスト剥離剤組成物(比較例11)、3級アルカノールアミンと、水溶性有機溶剤と、窒素原子を1個のみ有するアミノ酸を含有するフォトレジスト剥離剤組成物(比較例7、8)、分子内にチオール基及びアミド構造を有せず、窒素原子を2個以上有するアミノ酸と水からなるフォトレジスト剥離剤組成物(比較例14、15)、分子内にチオール基及びアミド構造を持たず、窒素原子を2個以上有するがアミド構造を有するアミノ酸(アスパラギン)を使用した組成物(比較例21)は、評価1において銅単膜の防食性が不良(評価「×」)であった。 As a result of the evaluation, a photoresist stripper composition containing a primary alkanolamine (Comparative Examples 1 and 3), which contains an amino acid having no thiol group and amide structure in the molecule and having two or more nitrogen atoms. Photoresist stripper composition containing primary alkanolamine (Comparative Example 10), 0.1% by weight of amino acid having no thiol group and amide structure in the molecule and having 2 or more nitrogen atoms Exceeding photoresist stripper composition (Comparative Examples 4, 6, 18-20), secondary alkanolamine and water-soluble organic solvent, but no thiol group or amide structure in the molecule, nitrogen Photoresist stripper composition not containing amino acid having 2 or more atoms (Comparative Example 17), tertiary alkanolamine, thiol group and amide structure in the molecule, Photoresist stripping composition containing alkanolamine having 2 or more atoms but no water-soluble organic solvent (Comparative Example 11), tertiary alkanolamine, water-soluble organic solvent, and only one nitrogen atom Photoresist stripper composition containing amino acids having (Comparative Examples 7 and 8), Photoresist stripper composition comprising an amino acid having two or more nitrogen atoms and water having no thiol group and amide structure in the molecule (Comparative Examples 14 and 15), a composition (Comparative Example 21) using an amino acid (asparagine) having no thiol group and amide structure in the molecule and having two or more nitrogen atoms but having an amide structure was evaluated as 1 The corrosion resistance of the copper single film was poor (evaluation “×”).
また、2級アルカノールアミン及び/または3級アルカノールアミンと水溶性有機溶剤を含有するが、分子内にチオール基及びアミド構造を有せず、窒素原子を2個以上有するアミノ酸を含有しないフォトレジスト剥離剤組成物(比較例5、9、16)と、アルミニウム防食性の防食剤(特開2001−350276号公報記載のもの)を含有するフォトレジスト剥離剤組成物(比較例12)、特許文献1記載の防食剤を含有するフォトレジスト剥離剤組成物(比較例13)は、評価2のCu/Mo配線防食性において銅(Cu)又はモリブデン(Mo)防食性が不十分(評価「△」)であった。 Photoresist stripping that contains secondary alkanolamine and / or tertiary alkanolamine and a water-soluble organic solvent, but has no thiol group or amide structure in the molecule and no amino acid having two or more nitrogen atoms Composition (Comparative Examples 5, 9, 16) and a photoresist stripper composition (Comparative Example 12) containing an aluminum anticorrosive anticorrosive (described in JP-A-2001-350276), Patent Document 1 The photoresist stripper composition (Comparative Example 13) containing the described anticorrosive has insufficient copper (Cu) or molybdenum (Mo) anticorrosion in the Cu / Mo wiring anticorrosion of Evaluation 2 (Evaluation “Δ”) Met.
水溶性有機溶剤のみからなるフォトレジスト剥離剤組成物(比較例2)は、評価1の銅単膜防食性、評価2のCu/Mo配線防食性ともに良好であったが、5%水溶液のpHが8以下であり、評価3のフォトレジスト剥離性が不十分(評価「△」)であった。分子内にチオール基及びアミド構造を有せず、窒素原子を2個以上有するアミノ酸と水からなるフォトレジスト剥離剤組成物(比較例14、15)も、5%水溶液のpHが8以下であり、評価3のフォトレジスト剥離性が不良(評価「×」)であった。 The photoresist stripper composition (Comparative Example 2) consisting only of a water-soluble organic solvent was good in both the copper single-film corrosion resistance of Evaluation 1 and the Cu / Mo wiring corrosion resistance of Evaluation 2, but the pH of a 5% aqueous solution Was 8 or less, and the photoresist peelability of evaluation 3 was insufficient (evaluation “Δ”). A photoresist remover composition (Comparative Examples 14 and 15) composed of an amino acid having two or more nitrogen atoms and water having no thiol group and amide structure in the molecule (Comparative Examples 14 and 15) also has a pH of 5% aqueous solution of 8 or less. The photoresist peelability of evaluation 3 was poor (evaluation “x”).
一方、本発明のフォトレジスト剥離剤組成物(実施例1〜17)は、評価1の銅単膜防食性、評価2のCu/Mo配線防食性、評価3のフォトレジスト剥離性のすべてにおいて良好(評価「○」)な結果が得られた。 On the other hand, the photoresist stripping compositions (Examples 1 to 17) of the present invention are good in all of the copper single film corrosion resistance of evaluation 1, the Cu / Mo wiring corrosion resistance of evaluation 2, and the photoresist peelability of evaluation 3. (Evaluation “◯”) was obtained.
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US11149235B2 (en) | 2018-07-20 | 2021-10-19 | Entegris, Inc. | Cleaning composition with corrosion inhibitor |
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