JP7490834B2 - How to remove the resin mask - Google Patents
How to remove the resin mask Download PDFInfo
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- JP7490834B2 JP7490834B2 JP2023008303A JP2023008303A JP7490834B2 JP 7490834 B2 JP7490834 B2 JP 7490834B2 JP 2023008303 A JP2023008303 A JP 2023008303A JP 2023008303 A JP2023008303 A JP 2023008303A JP 7490834 B2 JP7490834 B2 JP 7490834B2
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- 239000011347 resin Substances 0.000 title claims description 144
- 229920005989 resin Polymers 0.000 title claims description 144
- 238000004140 cleaning Methods 0.000 claims description 110
- 239000000203 mixture Substances 0.000 claims description 110
- 238000000034 method Methods 0.000 claims description 74
- 239000007788 liquid Substances 0.000 claims description 40
- 238000002161 passivation Methods 0.000 claims description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000012459 cleaning agent Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- -1 ethyleneoxy group Chemical group 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 13
- 239000000908 ammonium hydroxide Substances 0.000 claims description 12
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000004380 ashing Methods 0.000 claims description 4
- 238000001312 dry etching Methods 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 229920006254 polymer film Polymers 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 16
- 229920002120 photoresistant polymer Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920002577 polybenzoxazole Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- JWKSQNWLEIABLH-UHFFFAOYSA-N 1-octan-2-yloxydodecane Chemical compound CCCCCCCCCCCCOC(C)CCCCCC JWKSQNWLEIABLH-UHFFFAOYSA-N 0.000 description 1
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 1
- ZFDNAYFXBJPPEB-UHFFFAOYSA-M 2-hydroxyethyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCO ZFDNAYFXBJPPEB-UHFFFAOYSA-M 0.000 description 1
- SHAMRMCOVNDTCS-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC(O)C[N+](C)(C)C SHAMRMCOVNDTCS-UHFFFAOYSA-M 0.000 description 1
- YSDSJBOULHYPCB-UHFFFAOYSA-M 2-hydroxypropyl(tripropyl)azanium hydroxide Chemical compound [OH-].OC(C[N+](CCC)(CCC)CCC)C YSDSJBOULHYPCB-UHFFFAOYSA-M 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RKTGAWJWCNLSFX-UHFFFAOYSA-M bis(2-hydroxyethyl)-dimethylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(C)CCO RKTGAWJWCNLSFX-UHFFFAOYSA-M 0.000 description 1
- IUEJJWYUYRJJBJ-UHFFFAOYSA-M bis(2-hydroxyethyl)-dipropylazanium hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCO)CCO IUEJJWYUYRJJBJ-UHFFFAOYSA-M 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- MYRLVAHFNOAIAI-UHFFFAOYSA-M diethyl-bis(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].OCC[N+](CC)(CC)CCO MYRLVAHFNOAIAI-UHFFFAOYSA-M 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- KGVNNTSVYGJCRV-UHFFFAOYSA-M ethyl-tris(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].OCC[N+](CC)(CCO)CCO KGVNNTSVYGJCRV-UHFFFAOYSA-M 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 150000004680 hydrogen peroxides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical class O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- VHLDQAOFSQCOFS-UHFFFAOYSA-M tetrakis(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].OCC[N+](CCO)(CCO)CCO VHLDQAOFSQCOFS-UHFFFAOYSA-M 0.000 description 1
- MSSZNJYLEVGNAK-UHFFFAOYSA-M tetrakis(2-hydroxypropyl)azanium;hydroxide Chemical compound [OH-].CC(O)C[N+](CC(C)O)(CC(C)O)CC(C)O MSSZNJYLEVGNAK-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GRNRCQKEBXQLAA-UHFFFAOYSA-M triethyl(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CCO GRNRCQKEBXQLAA-UHFFFAOYSA-M 0.000 description 1
- RBUVMOSJYGXQEK-UHFFFAOYSA-M triethyl(2-hydroxypropyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC(C)O RBUVMOSJYGXQEK-UHFFFAOYSA-M 0.000 description 1
- IJGSGCGKAAXRSC-UHFFFAOYSA-M tris(2-hydroxyethyl)-methylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(CCO)CCO IJGSGCGKAAXRSC-UHFFFAOYSA-M 0.000 description 1
- FQSMVJXSANYLPV-UHFFFAOYSA-M tris(2-hydroxyethyl)-propylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCO)(CCO)CCO FQSMVJXSANYLPV-UHFFFAOYSA-M 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Detergent Compositions (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
Description
本開示は、樹脂マスクの剥離方法に関する。 This disclosure relates to a method for removing a resin mask.
近年、パーソナルコンピュータや各種電子デバイスにおいては、低消費電力化、処理速度の高速化、小型化が進み、これらに搭載されるパッケージ基板などの配線は年々微細化が進んでいる。このような微細配線並びにピラーやバンプといった接続端子形成にはこれまでメタルマスク法が主に用いられてきたが、汎用性が低いことや配線等の微細化への対応が困難になってきたことから、他の新たな方法へと変わりつつある。 In recent years, personal computers and various electronic devices have become more energy efficient, faster, and smaller, and the wiring on package boards and other devices mounted on these devices is becoming finer every year. Until now, the metal mask method has been the main method used to form such fine wiring and connection terminals such as pillars and bumps, but due to its low versatility and the difficulty of dealing with the miniaturization of wiring, etc., new methods are being used.
新たな方法の一つとして、ドライフィルムレジストをメタルマスクに代えて厚膜樹脂マスクとして使用する方法が知られている。この樹脂マスクは最終的に剥離・除去されるが、剥離・除去等の洗浄に使用する洗浄剤として、アルカリ剤と水とを含む樹脂マスク剥離用洗浄剤が知られている。 One of the new methods is to use a dry film resist as a thick resin mask instead of a metal mask. This resin mask is eventually peeled off and removed, and a cleaning agent for peeling off the resin mask that contains an alkaline agent and water is known as a cleaning agent used for the peeling and removal.
例えば、特許文献１には、ドライエッチング工程後の半導体デバイスの洗浄に用いる洗浄液として、ヒドロキシルアミン等の還元剤、及び、界面活性剤を含み、ｐＨが１０～１４の半導体デバイス用洗浄液が記載されている。そして、特許文献１では、ドライエッチング工程およびドライアッシング工程後のフォトレジスト残渣、エッチング残渣、反射防止膜、アッシング残渣を洗浄対象としている。 For example, Patent Document 1 describes a cleaning solution for semiconductor devices that contains a reducing agent such as hydroxylamine and a surfactant and has a pH of 10 to 14 as a cleaning solution used to clean semiconductor devices after a dry etching process. Patent Document 1 also describes photoresist residues, etching residues, anti-reflective films, and ashing residues after the dry etching process and dry ashing process as targets for cleaning.
プリント基板等に微細配線を形成する上で、樹脂マスクの残存はもちろんのこと、微細配線やピラー、バンプ形成に用いられるはんだやめっき液等に含まれる助剤等の残存を低減するため、洗浄剤組成物には高い洗浄性が要求される。
ここで、樹脂マスクとは、光や電子線等によって現像液に対する溶解性等の物性が変化するレジストを用いて形成されるものである。このような特性を有する樹脂マスクを使用することで、金属配線、金属ピラーやハンダバンプといった回路基板の微細な接続部を形成することができる。
When forming fine wiring on printed circuit boards and the like, a cleaning composition is required to have high cleaning properties in order to reduce not only the residue of a resin mask but also the residue of auxiliary agents contained in solder and plating solutions used in forming the fine wiring, pillars, and bumps.
Here, the resin mask is formed using a resist whose physical properties, such as solubility in a developer, change when exposed to light, electron beams, etc. By using a resin mask having such properties, it is possible to form fine connections on a circuit board, such as metal wiring, metal pillars, and solder bumps.
しかしながら、配線やピラー、パンプが微細化するにつれて、これらの間隔も微細となり、微細な隙間にある樹脂マスクを除去することが困難になってきており、洗浄剤組成物には、高い樹脂マスク剥離性が要求される。
さらに、基板の変化とともに高層ピラーの形成が必要とされており、厚さが１００μｍを超えるようなレジスト（樹脂マスク）が使われるようになってきている。また、配線幅に対して厚さがある、アスペクト比の高いレジストパターンを作製するため、高硬度のレジストが用いられるようになってきている。そのため、例えば、厚さ１００μｍ以上で高硬度のレジスト膜（樹脂マスク）を剥離可能な洗浄剤組成物が求められている。
However, as wiring, pillars, and bumps become finer, the spaces between them also become finer, making it difficult to remove the resin mask in these fine gaps. For this reason, cleaning compositions are required to have high resin mask strippability.
Furthermore, with the change in substrate, the formation of high-rise pillars is required, and resists (resin masks) having a thickness of more than 100 μm are being used. Also, in order to prepare resist patterns having a high aspect ratio and a thickness relative to the wiring width, resists having high hardness are being used. Therefore, there is a demand for a cleaning composition capable of stripping a resist film (resin mask) having a thickness of 100 μm or more and high hardness.
そこで、本開示は、一態様において、厚さ１００μｍ以上の樹脂マスクの剥離性に優れる樹脂マスクの剥離方法を提供する。 Therefore, in one aspect, the present disclosure provides a method for peeling a resin mask that has excellent peelability for a resin mask having a thickness of 100 μm or more.
本開示は、一態様において、洗浄剤組成物を用いて、樹脂マスクを有する基板から樹脂マスクを剥離する工程を含み、樹脂マスクの厚さが１００μｍ以上であり、前記洗浄剤組成物は、下記成分Ａ、下記成分Ｂ、下記成分Ｃ及び下記成分Ｄを含有する水系洗浄剤であり、前記洗浄剤組成物中の成分Ｄの含有量が、６０質量％以上である、樹脂マスクの剥離方法に関する。
成分Ａ：第４級アンモニウム水酸化物
成分Ｂ：ヒドロキシルアミン
成分Ｃ：水酸化カリウム
成分Ｄ：水
In one aspect, the present disclosure relates to a method for stripping a resin mask, the method including a step of stripping the resin mask from a substrate having the resin mask by using a cleaning composition, the resin mask having a thickness of 100 μm or more, the cleaning composition being an aqueous cleaning agent containing the following components A, B, C, and D, and the content of component D in the cleaning composition is 60 mass% or more.
Component A: Quaternary ammonium hydroxide Component B: Hydroxylamine Component C: Potassium hydroxide Component D: Water
本開示によれば、一態様において、厚さ１００μｍ以上の樹脂マスクの剥離性に優れる樹脂マスクの剥離方法を提供できる。 In one aspect, the present disclosure provides a method for removing a resin mask that has excellent peelability for a resin mask having a thickness of 100 μm or more.
本開示は、第４級アンモニウム水酸化物とヒドロキシルアミンと水酸化カリウムを含む洗浄剤組成物を用いることで、厚さ１００μｍ以上の樹脂マスクを効率よく剥離できるという知見に基づく。 This disclosure is based on the finding that a resin mask having a thickness of 100 μm or more can be efficiently stripped by using a cleaning composition containing quaternary ammonium hydroxide, hydroxylamine, and potassium hydroxide.
本開示は、一態様において、洗浄剤組成物を用いて、樹脂マスクを有する基板から樹脂マスクを剥離する工程を含み、樹脂マスクの厚さが１００μｍ以上であり、前記洗浄剤組成物は、下記成分Ａ、下記成分Ｂ、下記成分Ｃ及び下記成分Ｄを含有する水系洗浄剤（以下、「本開示の洗浄剤組成物」ともいう）であり、前記洗浄剤組成物中の成分Ｄの含有量が、６０質量％以上である、樹脂マスクの剥離方法（以下、「本開示の剥離方法」ともいう）に関する。
成分Ａ：第４級アンモニウム水酸化物
成分Ｂ：ヒドロキシルアミン
成分Ｃ：水酸化カリウム
成分Ｄ：水
In one aspect, the present disclosure relates to a method for stripping a resin mask (hereinafter also referred to as the "stripping method of the present disclosure"), the method including a step of stripping a resin mask from a substrate having the resin mask by using a cleaning composition, the resin mask having a thickness of 100 µm or more, the cleaning composition being an aqueous cleaning agent containing the following components A, B, C, and D (hereinafter also referred to as the "cleaning composition of the present disclosure"), and the cleaning composition having a content of component D of 60 mass% or more.
Component A: Quaternary ammonium hydroxide Component B: Hydroxylamine Component C: Potassium hydroxide Component D: Water
本開示によれば、厚さ１００μｍ以上の樹脂マスクの剥離性に優れる樹脂マスクの剥離方法を提供できる。そして、本開示の剥離方法を用いることによって、高い収率で高品質の電子部品を得ることができる。 According to the present disclosure, a method for peeling a resin mask that has excellent peelability for resin masks with a thickness of 100 μm or more can be provided. Furthermore, by using the peeling method of the present disclosure, high-quality electronic components can be obtained with a high yield.
本開示の効果発現の作用メカニズムの詳細は不明な部分があるが、以下のように推定される。
第４級アンモニウム水酸化物（成分Ａ）及び水酸化カリウム（成分Ｃ）は樹脂マスク内に浸透して樹脂マスクに配合されているアルカリ可溶性樹脂の解離を促進し、更に解離によって生じる電荷の反発を起こすことによって樹脂マスクの剥離を促進すると考えられる。そして、第４級アンモニウム水酸化物（成分Ａ）と水酸化カリウム（成分Ｃ）では、樹脂マスクへの浸透速度が異なるため、樹脂マスク表面のアルカリ可溶性樹脂が急激に解離することを抑制し、浸透阻害となる樹脂マスク表面のみの電荷反発が抑制されると考えられる。
一方で、ヒドロキシルアミン（成分Ｂ）は第４級アンモニウム水酸化物（成分Ａ）及び水酸化カリウム（成分Ｃ）と共に樹脂マスクへ浸透し、浸透を促進してアルカリ可溶性樹脂の剥離性をさらに促進すると考えられる。
但し、本開示はこのメカニズムに限定して解釈されなくてもよい。
Although the details of the mechanism of action by which the effects of the present disclosure are expressed are unclear, it is presumed as follows.
It is believed that the quaternary ammonium hydroxide (component A) and potassium hydroxide (component C) penetrate into the resin mask to promote dissociation of the alkali-soluble resin contained in the resin mask, and further promote peeling of the resin mask by causing repulsion of the electric charges generated by the dissociation. Since the quaternary ammonium hydroxide (component A) and potassium hydroxide (component C) have different penetration rates into the resin mask, it is believed that the alkali-soluble resin on the surface of the resin mask is prevented from suddenly dissociating, and the electric charge repulsion only on the surface of the resin mask, which is an impediment to penetration, is suppressed.
On the other hand, it is believed that hydroxylamine (component B) penetrates into the resin mask together with the quaternary ammonium hydroxide (component A) and potassium hydroxide (component C), promoting penetration and further enhancing the strippability of the alkali-soluble resin.
However, the present disclosure need not be construed as being limited to this mechanism.
本開示において、樹脂マスクとは、エッチング、めっき、加熱等の処理から物質表面を保護するためのマスク、すなわち、保護膜として機能するマスクである。樹脂マスクとしては、一又は複数の実施形態において、露光及び現像工程後のレジスト層、露光及び現像の少なくとも一方の処理が施された（以下、「露光及び／又は現像処理された」ともいう）レジスト層、あるいは、硬化したレジスト層が挙げられる。
また、樹脂マスクは、光や電子線等によって現像液に対する溶解性等の物性が変化するレジストを用いて形成される。レジストは、光や電子線との反応方法から、ネガ型とポジ型に大きく分けられている。レジストは、光や電子線との反応方法から、ネガ型とポジ型に大きく分けられている。ネガ型レジストは、露光されると現像液に対する溶解性が低下する特性を有し、ネガ型レジストを含む層（以下、「ネガ型レジスト層」ともいう）は、露光及び現像処理後に露光部が樹脂マスクとして使用される。ポジ型レジストは、露光されると現像液に対する溶解性が増大する特性を有し、ポジ型レジストを含む層（以下、「ポジ型レジスト層」ともいう）は、露光及び現像処理後に露光部が除去され、未露光部が樹脂マスクとして使用される。このような特性を有する樹脂マスクを使用することで、金属配線、金属ピラーやハンダバンプといった回路基板の微細な接続部を形成することができる。
樹脂マスクを形成する樹脂材料としては、一又は複数の実施形態において、フィルム状の感光性樹脂、レジストフィルム、又はフォトレジストが挙げられる。レジストフィルムは汎用のものを使用でき、ネガ型レジストフィルムが好ましい。
樹脂マスクとしては、例えば、アクリル酸系ポリマー膜が挙げられる。
高層ピラーの形成が必要とされる場合、樹脂マスクとしては、例えば、厚さが１００μｍを超えるようなレジスト（樹脂マスク）を用いることが好ましい。また、配線幅やピラーピッチ、バンプピッチに対して厚さがある、アスペクト比の高いレジストパターンを作製する場合、樹脂マスクとしては、例えば、高硬度のレジストを用いることが好ましい。ここで、配線幅やピラーピッチ、バンプピッチに対して厚さがある、アスペクト比の高いレジストパーンとは、例えば、レジストにパターンニングを行って円柱状の穴を形成し、その穴の中に銅めっき処理により銅を成膜して生じる銅ピラーのパターンが挙げられる。
In the present disclosure, a resin mask is a mask for protecting a surface of a material from treatments such as etching, plating, heating, etc., that is, a mask that functions as a protective film. In one or more embodiments, the resin mask may be a resist layer after exposure and development steps, a resist layer that has been subjected to at least one of exposure and development (hereinafter also referred to as "exposed and/or developed"), or a hardened resist layer.
The resin mask is formed using a resist whose physical properties, such as solubility in a developer, change due to light or an electron beam. Resists are largely divided into negative and positive types based on the reaction method with light or an electron beam. Resists are largely divided into negative and positive types based on the reaction method with light or an electron beam. A negative resist has a property that its solubility in a developer decreases when exposed to light, and the exposed portion of a layer containing a negative resist (hereinafter also referred to as a "negative resist layer") is used as a resin mask after exposure and development processing. A positive resist has a property that its solubility in a developer increases when exposed to light, and the exposed portion of a layer containing a positive resist (hereinafter also referred to as a "positive resist layer") is removed after exposure and development processing, and the unexposed portion is used as a resin mask. By using a resin mask having such properties, fine connections of a circuit board, such as metal wiring, metal pillars, and solder bumps, can be formed.
In one or more embodiments, the resin material for forming the resin mask may be a film-like photosensitive resin, a resist film, or a photoresist. A general-purpose resist film may be used, and a negative resist film is preferable.
The resin mask may be, for example, an acrylic acid-based polymer film.
When it is necessary to form a high-rise pillar, it is preferable to use a resist (resin mask) having a thickness of, for example, more than 100 μm as the resin mask. In addition, when preparing a resist pattern having a high aspect ratio, which is thicker than the wiring width, pillar pitch, and bump pitch, it is preferable to use a resist having high hardness as the resin mask. Here, the resist pattern having a high aspect ratio, which is thicker than the wiring width, pillar pitch, and bump pitch, is, for example, a copper pillar pattern formed by forming a cylindrical hole by patterning the resist and depositing copper in the hole by copper plating.
[剥離工程]
本開示の剥離方法は、本開示の洗浄剤組成物を用いて、樹脂マスクを有する基板（被洗浄物）から樹脂マスクを剥離する工程（以下、単に「剥離工程」ともいう）を含む。
前記剥離工程は、一又は複数の実施形態において、被洗浄物を本開示の洗浄剤組成物に接触させることを含む。
[Peeling process]
The stripping method of the present disclosure includes a step of stripping a resin mask from a substrate (object to be cleaned) having the resin mask thereon by using the cleaning composition of the present disclosure (hereinafter also simply referred to as a "stripping step").
In one or more embodiments, the peeling step includes contacting the object to be cleaned with the cleaning composition of the present disclosure.
本開示の洗浄剤組成物を用いて被洗浄物から樹脂マスクを剥離する方法、又は、被洗浄物に本開示の洗浄剤組成物を接触させる方法としては、例えば、洗浄剤組成物を入れた洗浄浴槽内へ浸漬することで接触させる方法、洗浄剤組成物をスプレー状に射出して接触させる方法（シャワー方式）、浸漬中に超音波照射する超音波洗浄方法等が挙げられる。本開示の洗浄剤組成物は、希釈することなくそのまま洗浄に使用できる。被洗浄物としては、後述する被洗浄物を挙げることができる。 Methods for peeling off a resin mask from an object to be cleaned using the cleaning composition of the present disclosure, or methods for bringing the cleaning composition of the present disclosure into contact with the object to be cleaned, include, for example, a method of contacting the object by immersing the object in a cleaning bath containing the cleaning composition, a method of contacting the object by spraying the cleaning composition in a spray form (shower method), and an ultrasonic cleaning method of irradiating the object with ultrasonic waves during immersion. The cleaning composition of the present disclosure can be used for cleaning as is without dilution. Examples of objects to be cleaned include the objects to be cleaned described below.
本開示の剥離方法は、一又は複数の実施形態において、洗浄剤組成物に被洗浄物を接触させた後、水でリンスし、乾燥する工程を含むことができる。本開示の剥離方法は、一又は複数の実施形態において、洗浄剤組成物に被洗浄物を接触させた後、水ですすぐ工程を含むことができる。 In one or more embodiments, the stripping method of the present disclosure may include a step of contacting the object to be cleaned with the cleaning composition, rinsing with water, and drying. In one or more embodiments, the stripping method of the present disclosure may include a step of contacting the object to be cleaned with the cleaning composition, and rinsing with water.
本開示の剥離方法は、本開示の洗浄剤組成物の洗浄力が発揮されやすい点から、本開示の洗浄剤組成物と被洗浄物との接触時に超音波を照射することが好ましく、その超音波は比較的高周波数であることがより好ましい。前記超音波の照射条件は、同様の観点から、例えば、２６～７２ｋＨｚ、８０～１５００Ｗが好ましく、３６～７２ｋＨｚ、８０～１５００Ｗがより好ましい。 In the stripping method of the present disclosure, it is preferable to irradiate ultrasonic waves when the cleaning composition of the present disclosure comes into contact with the object to be cleaned, since this makes it easier for the cleaning power of the cleaning composition of the present disclosure to be exerted, and it is more preferable that the ultrasonic waves have a relatively high frequency. From the same viewpoint, the ultrasonic irradiation conditions are, for example, preferably 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.
本開示の剥離方法において、本開示の洗浄剤組成物の洗浄力が発揮されやすい点から、洗浄剤組成物の温度は４０℃以上が好ましく、５０℃以上がより好ましく、そして、パッシベーション膜へのダメージ抑制の観点から、基板に対する影響低減の観点から、７０℃以下が好ましく、６０℃以下がより好ましい。 In the stripping method of the present disclosure, the temperature of the cleaning composition is preferably 40°C or higher, more preferably 50°C or higher, in order to allow the cleaning power of the cleaning composition of the present disclosure to be easily exerted, and from the viewpoint of suppressing damage to the passivation film and reducing the effect on the substrate, the temperature is preferably 70°C or lower, more preferably 60°C or lower.
［被洗浄物］
被洗浄物としては、一又は複数の実施形態において、樹脂マスクを有する基板、パッシベーション膜及び樹脂マスクを有する基板等が挙げられる。樹脂マスクを剥離しつつパッシベーション膜のしわや欠落を抑制できる観点から、樹脂マスクを有する基板は、一又は複数の実施形態において、更にパッシベーション膜を有する基板が好ましい。基板としては、プリント基板、ウエハ、銅板及びアルミニウム板等が挙げられる。
[Item to be cleaned]
In one or more embodiments, the object to be cleaned may be a substrate having a resin mask, a substrate having a passivation film and a resin mask, etc. In one or more embodiments, the substrate having a resin mask is preferably a substrate further having a passivation film, from the viewpoint of being able to suppress wrinkles or chipping of the passivation film while peeling off the resin mask. Examples of the substrate include a printed circuit board, a wafer, a copper plate, and an aluminum plate.
被洗浄物としては、一又は複数の実施形態において、樹脂マスクが付着した被洗浄物が挙げられる。樹脂マスクが付着した被洗浄物としては、一又は複数の実施形態において、樹脂マスクを有する電子部品及びその製造中間物、パッシベーション膜及び樹脂マスクを有する電子部品及びその製造中間物等が挙げられる。電子部品としては、例えば、プリント基板、ウエハ、銅板及びアルミニウム板等の金属板から選ばれる少なくとも１つの部品が挙げられる。前記製造中間物は、電子部品の製造工程における中間製造物であって、樹脂マスク処理後の中間製造物を含む。
樹脂マスクが付着した被洗浄物の具体例としては、例えば、基板上に配線を形成する配線形成工程、配線が形成された基板にパッシベーション膜を形成するパッシベーション膜形成工程、パッシベーション膜上にレジストを塗布し、現像及び／又は露光処理し、パターン化されたレジスト膜を形成するレジスト膜形成工程、パターン化されたレジスト膜をマスクとしてパッシベーション膜をエッチングするエッチング工程を経ることにより得られた基板に、レジスト膜（樹脂マスク）を付与したパッシベーション膜を有する電子部品が挙げられる。また、被洗浄物は、樹脂マスクの剥離性の観点から、樹脂マスクが露光及び／又は現像処理された後にドライエッチング工程やドライアッシング工程を経ないものが好ましい。
In one or more embodiments, the object to be cleaned may include an object to be cleaned with a resin mask attached thereto. In one or more embodiments, the object to be cleaned with a resin mask attached may include an electronic component having a resin mask and its manufacturing intermediate, an electronic component having a passivation film and a resin mask and its manufacturing intermediate, etc. Examples of the electronic component include at least one component selected from a printed circuit board, a wafer, and a metal plate such as a copper plate or an aluminum plate. The manufacturing intermediate is an intermediate product in the manufacturing process of an electronic component, and includes an intermediate product after a resin mask treatment.
Specific examples of the object to be cleaned with a resin mask attached include an electronic component having a passivation film obtained by applying a resist film (resin mask) to a substrate obtained by passing through a wiring forming process for forming wiring on a substrate, a passivation film forming process for forming a passivation film on a substrate on which wiring has been formed, a resist film forming process for applying a resist on a passivation film, developing and/or exposing the resist film to form a patterned resist film, and an etching process for etching the passivation film using the patterned resist film as a mask. From the viewpoint of the peelability of the resin mask, it is preferable that the object to be cleaned does not pass through a dry etching process or a dry ashing process after the resin mask is exposed and/or developed.
樹脂マスクとしては、例えば、ネガ型樹脂マスクでもよいし、ポジ型樹脂マスクでもよい。本開示においてネガ型樹脂マスクとは、ネガ型レジストを用いて形成されるものであり、例えば、露光及び／又は現像処理されたネガ型レジスト層が挙げられる。本開示においてポジ型樹脂マスクとは、ポジ型レジストを用いて形成されるものであり、例えば、露光及び／又は現像処理されたポジ型レジスト層が挙げられる。本開示の樹脂マスクの剥離方法では、配線やピラー、バンプ等の隙間にある樹脂マスクを剥離することができ、樹脂マスクの剥離性を発揮する観点から、ネガ型レジスト層を洗浄対象とすることが好ましい。
樹脂マスクの厚さは、一又は複数の実施形態において、１００μｍ以上であり、厚くても剥離できる観点から、好ましくは１５０μｍ以上、より好ましくは２００μｍ以上である。また、樹脂マスクの厚さは、剥離性の観点から、好ましくは５００μｍ以下、より好ましくは３５０μｍ以下である。
配線の隙間は、樹脂マスクの剥離性の観点から、好ましくは３０μｍ以上、より好ましくは１００μｍ以上であり、そして、好ましくは５００μｍ以下、より好ましくは３００μｍ以下である。
ピラー及びバンプのピッチ（隙間）は、樹脂マスクの剥離性の観点から、好ましくは１００μｍ以上、より好ましくは１５０μｍ以上であり、そして、好ましくは１０００μｍ以下、より好ましくは５００μｍ以下である。
The resin mask may be, for example, a negative resin mask or a positive resin mask. In the present disclosure, the negative resin mask is formed using a negative resist, and examples of the negative resin mask include a negative resist layer that has been exposed and/or developed. In the present disclosure, the positive resin mask is formed using a positive resist, and examples of the positive resin mask include a positive resist layer that has been exposed and/or developed. In the resin mask stripping method of the present disclosure, the resin mask in the gaps between wiring, pillars, bumps, etc. can be stripped, and from the viewpoint of exerting the strippability of the resin mask, it is preferable to clean the negative resist layer.
In one or more embodiments, the thickness of the resin mask is 100 μm or more, and from the viewpoint of being able to be peeled off even if it is thick, the thickness is preferably 150 μm or more, more preferably 200 μm or more. In addition, from the viewpoint of peelability, the thickness of the resin mask is preferably 500 μm or less, more preferably 350 μm or less.
From the viewpoint of peelability of the resin mask, the gap between the wirings is preferably 30 μm or more, more preferably 100 μm or more, and is preferably 500 μm or less, more preferably 300 μm or less.
From the viewpoint of peelability of the resin mask, the pitch (gap) of the pillars and bumps is preferably 100 μm or more, more preferably 150 μm or more, and preferably 1000 μm or less, more preferably 500 μm or less.
本開示において、パッシベーション膜とは、一又は複数の実施形態において、半導体素子を外的損傷から保護する表面保護膜である。
パッシベーション膜としては、ポリイミド（ＰＩ）系ポリマー、ポリベンゾオキサゾール（ＰＢＯ）系ポリマー、及びシリコーン系ポリマーから選ばれる少なくとも１種のポリマー膜が挙げられる。
パッシベーション膜の厚さとしては、例えば、５μｍ以上２０μｍ以下が挙げられ、薄くても樹脂マスク剥離の際にダメージを抑制できる観点から、好ましくは１２μｍ以下、より好ましくは１０μｍ以下である。
In the present disclosure, in one or more embodiments, a passivation film is a surface protection film that protects a semiconductor element from external damage.
The passivation film may be at least one polymer film selected from the group consisting of polyimide (PI)-based polymers, polybenzoxazole (PBO)-based polymers, and silicone-based polymers.
The thickness of the passivation film is, for example, from 5 μm to 20 μm, and is preferably 12 μm or less, and more preferably 10 μm or less, from the viewpoint of suppressing damage when peeling off the resin mask even if the thickness is thin.
［洗浄剤組成物］
本開示の洗浄剤組成物は、一又は複数の実施形態において、下記成分Ａ、下記成分Ｂ、下記成分Ｃ及び下記成分Ｄを含有する水系洗浄剤である。
[Cleaning agent composition]
In one or more embodiments, the cleaning composition of the present disclosure is an aqueous cleaning agent containing the following component A, the following component B, the following component C, and the following component D.
（成分Ａ：第４級アンモニウム水酸化物）
本開示の洗浄剤組成物に含まれる第４級アンモニウム水酸化物（以下、単に「成分Ａ」ともいう）としては、一又は複数の実施形態において、例えば、下記式（Ｉ）で表される第４級アンモニウム水酸化物が挙げられる。成分Ａは、１種でもよいし、２種以上の組合せでもよい。
In one or more embodiments, the quaternary ammonium hydroxide contained in the cleaning composition of the present disclosure (hereinafter, also simply referred to as "Component A") may be, for example, a quaternary ammonium hydroxide represented by the following formula (I). Component A may be one type or a combination of two or more types.
上記式（Ｉ）において、Ｒ1、Ｒ2、Ｒ3及びＲ4は、それぞれ独立に、メチル基、エチル基、プロピル基、ヒドロキシメチル基、ヒドロキシエチル基及びヒドロキシプロピル基から選ばれる少なくとも１種である。 In the above formula (I), R 1 , R 2 , R 3 and R 4 each independently represent at least one group selected from a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group and a hydroxypropyl group.
式（Ｉ）で表される第４級アンモニウム水酸化物としては、例えば、第４級アンモニウムカチオンとヒドロキシドとからなる塩等が挙げられる。第４級アンモニウム水酸化物としては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、２－ヒドロキシエチルトリメチルアンモニウムヒドロキシド（コリン）、２－ヒドロキシエチルトリエチルアンモニウムヒドロキシド、２－ヒドロキシエチルトリプロピルアンモニウムヒドロキシド、２－ヒドロキシプロピルトリメチルアンモニウムヒドロキシド、２－ヒドロキシプロピルトリエチルアンモニウムヒドロキシド、２－ヒドロキシプロピルトリプロピルアンモニウムヒドロキシド、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、ジエチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、ジプロピルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、トリス（２－ヒドロキシエチル）メチルアンモニウムヒドロキシド、トリス（２－ヒドロキシエチル）エチルアンモニウムヒドロキシド、トリス（２－ヒドロキシエチル）プロピルアンモニウムヒドロキシド、テトラキス（２－ヒドロキシエチル）アンモニウムヒドロキシド、及びテトラキス（２－ヒドロキシプロピル）アンモニウムヒドロキシドから選ばれる少なくとも１種が挙げられる。これらの中でも、樹脂マスク剥離性向上の観点から、テトラメチルアンモニウムヒドロキシド及びテトラエチルアンモニウムヒドロキシドが好ましく、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）がより好ましい。 Examples of the quaternary ammonium hydroxide represented by formula (I) include salts composed of a quaternary ammonium cation and a hydroxide. Examples of the quaternary ammonium hydroxide include at least one selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), 2-hydroxyethyltriethylammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, diethylbis(2-hydroxyethyl)ammonium hydroxide, dipropylbis(2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydroxide, tris(2-hydroxyethyl)propylammonium hydroxide, tetrakis(2-hydroxyethyl)ammonium hydroxide, and tetrakis(2-hydroxypropyl)ammonium hydroxide. Among these, from the viewpoint of improving the peelability of the resin mask, tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferred, and tetramethylammonium hydroxide (TMAH) is more preferred.
本開示の洗浄剤組成物中の成分Ａの含有量は、樹脂マスク剥離性の観点から、０．５質量％以上が好ましく、１．５質量％以上がより好ましく、２質量％以上が更に好ましく、そして、樹脂マスク剥離性の観点から、１０質量％以下が好ましく、８質量％以下がより好ましい。より具体的には、本開示の洗浄剤組成物中の成分Ａの含有量は、０．５質量％以上１０質量％以下が好ましく、１．５質量％以上８質量％以下がより好ましく、２質量％以上８質量％以下が更に好ましい。成分Ａが２種以上の組合せである場合、成分Ａの含有量はそれらの合計含有量をいう。
本開示の洗浄剤組成物中の成分Ａがテトラメチルアンモニウムヒドロキシドを含む場合、テトラメチルアンモニウムヒドロキシドの含有量は、樹脂マスク剥離性の観点から、０．５質量％以上が好ましく、１．５質量％以上がより好ましく、２質量％以上が更に好ましく、そして、樹脂マスク剥離性の観点から、１０質量％以下が好ましく、８質量％以下がより好ましい。より具体的には、本開示の洗浄剤組成物中のテトラメチルアンモニウムヒドロキシドの含有量は、０．５質量％以上１０質量％以下が好ましく、１．５質量％以上８質量％以下がより好ましく、２質量％以上８質量％以下が更に好ましい。
The content of component A in the cleaning composition of the present disclosure is preferably 0.5% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more from the viewpoint of resin mask peelability, and is preferably 10% by mass or less, and more preferably 8% by mass or less from the viewpoint of resin mask peelability. More specifically, the content of component A in the cleaning composition of the present disclosure is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1.5% by mass or more and 8% by mass or less, and even more preferably 2% by mass or more and 8% by mass or less. When component A is a combination of two or more types, the content of component A refers to the total content thereof.
When component A in the cleaning composition of the present disclosure contains tetramethylammonium hydroxide, the content of tetramethylammonium hydroxide is preferably 0.5% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more from the viewpoint of resin mask strippability, and is preferably 10% by mass or less, and more preferably 8% by mass or less from the viewpoint of resin mask strippability. More specifically, the content of tetramethylammonium hydroxide in the cleaning composition of the present disclosure is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1.5% by mass or more and 8% by mass or less, and even more preferably 2% by mass or more and 8% by mass or less.
（成分Ｂ：ヒドロキシルアミン）
本開示の洗浄剤組成物は、ヒドロキシルアミン（以下、「成分Ｂ」ともいう）を含有する。
本開示の洗浄剤組成物中の成分Ｂの含有量は、樹脂マスク剥離性の観点から、３質量％以上が好ましく、６質量％以上がより好ましく、７質量％以上が更に好ましく、８質量％以上が更に好ましく、そして、樹脂マスク剥離性の観点から、２０質量％以下が好ましく、１３質量％以下がより好ましい。より具体的には、本開示の洗浄剤組成物中の成分Ｂの含有量は、３質量％以上２０質量％以下が好ましく、６質量％以上１３質量％以下がより好ましく、７質量％以上１３質量％以下が更に好ましく、８質量％以上１３質量％以下が更に好ましい。
(Component B: Hydroxylamine)
The cleaning composition of the present disclosure contains a hydroxylamine (hereinafter also referred to as "component B").
The content of component B in the cleaning composition of the present disclosure is preferably 3% by mass or more, more preferably 6% by mass or more, even more preferably 7% by mass or more, and even more preferably 8% by mass or more from the viewpoint of resin mask strippability, and is preferably 20% by mass or less, and more preferably 13% by mass or less from the viewpoint of resin mask strippability. More specifically, the content of component B in the cleaning composition of the present disclosure is preferably 3% by mass or more and 20% by mass or less, more preferably 6% by mass or more and 13% by mass or less, even more preferably 7% by mass or more and 13% by mass or less, and even more preferably 8% by mass or more and 13% by mass or less.
（成分Ｃ：水酸化カリウム）
本開示の洗浄剤組成物は、水酸化カリウム（以下、「成分Ｃ」ともいう）を含有する。
本開示の洗浄剤組成物中の成分Ｃの含有量は、樹脂マスク剥離性の観点から、０．８質量％以上が好ましく、２質量％以上がより好ましく、３質量％以上が更に好ましく、そして、樹脂マスク剥離性の観点から、８質量％以下が好ましく、６質量％以下がより好ましい。より具体的には、本開示の洗浄剤組成物中の成分Ｃの含有量は、０．８質量％以上８質量％以下が好ましく、２質量％以上６質量％以下がより好ましく、３質量％以上６質量％以下が更に好ましい。
(Component C: Potassium hydroxide)
The cleaning composition of the present disclosure contains potassium hydroxide (hereinafter also referred to as "component C").
The content of component C in the cleaning composition of the present disclosure is preferably 0.8% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more from the viewpoint of resin mask strippability, and is preferably 8% by mass or less, more preferably 6% by mass or less from the viewpoint of resin mask strippability. More specifically, the content of component C in the cleaning composition of the present disclosure is preferably 0.8% by mass or more and 8% by mass or less, more preferably 2% by mass or more and 6% by mass or less, and even more preferably 3% by mass or more and 6% by mass or less.
本開示の洗浄剤組成物中の成分Ａと成分Ｃとの合計含有量は、樹脂マスク剥離性の観点から、３質量％以上が好ましく、４質量％以上がより好ましく、５質量％以上が更に好ましく、そして、樹脂マスク剥離性の観点から、１５質量％以下が好ましく、１３質量％以下がより好ましい。より具体的には、本開示の洗浄剤組成物中の成分Ａと成分Ｃとの合計含有量は、３質量％以上１５質量％以下が好ましく、４質量％以上１３質量％以下がより好ましく、５質量％以上１３質量％以下が更に好ましい。 The total content of component A and component C in the cleaning composition of the present disclosure is preferably 3% by mass or more, more preferably 4% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of resin mask peelability, and is preferably 15% by mass or less, and more preferably 13% by mass or less, from the viewpoint of resin mask peelability. More specifically, the total content of component A and component C in the cleaning composition of the present disclosure is preferably 3% by mass or more and 15% by mass or less, more preferably 4% by mass or more and 13% by mass or less, and even more preferably 5% by mass or more and 13% by mass or less.
本開示の洗浄剤組成物中の成分Ａの含有量に対する成分Ｃの含有量の質量比（Ｃ／Ａ）は、樹脂マスク剥離性の観点から、０．３以上が好ましく、１以上がより好ましく、１．５以上が更に好ましく、そして、樹脂マスク剥離性の観点から、８以下が好ましく、４以下がより好ましい。より具体的には、本開示の洗浄剤組成物中の質量比Ｃ／Ａは、０．３以上８以下が好ましく、１以上４以下がより好ましく、１．５以上４以下が更に好ましい。 The mass ratio (C/A) of the content of component C to the content of component A in the cleaning composition of the present disclosure is preferably 0.3 or more, more preferably 1 or more, and even more preferably 1.5 or more, from the viewpoint of resin mask peelability, and is preferably 8 or less, more preferably 4 or less, from the viewpoint of resin mask peelability. More specifically, the mass ratio C/A in the cleaning composition of the present disclosure is preferably 0.3 or more and 8 or less, more preferably 1 or more and 4 or less, and even more preferably 1.5 or more and 4 or less.
（成分Ｄ：水）
本開示の洗浄剤組成物に含まれる水（以下、「成分Ｄ」ともいう）としては、一又は複数の実施形態において、イオン交換水、ＲＯ水、蒸留水、純水、超純水等が挙げられる。
(Component D: Water)
In one or more embodiments, examples of water contained in the cleaning agent composition of the present disclosure (hereinafter also referred to as "component D") include ion-exchanged water, RO water, distilled water, pure water, and ultrapure water.
本開示の洗浄剤組成物中の成分Ｄの含有量は、成分Ａ、成分Ｂ、成分Ｃ及び後述する任意成分を除いた残余とすることができる。具体的には、本開示の洗浄剤組成物中の成分Ｄの含有量は、樹脂マスク剥離性向上、パッシベーション膜へのダメージ抑制、排水処理負荷低減、及び基板に対する影響低減の観点から、６０質量％以上であって、７０質量％以上が好ましく、８０質量％以上が更に好ましく、そして、樹脂マスク剥離性向上の観点から、９９質量％以下が好ましく、９８質量％以下がより好ましく、９７質量％以下が更に好ましい。より具体的には、本開示の洗浄剤組成物の使用時における成分Ｃの含有量は、６０質量％以上９９質量％以下が好ましく、７０質量％以上９８質量％以下がより好ましく、８０質量％以上９７質量％以下が更に好ましい。 The content of component D in the cleaning composition of the present disclosure can be the remainder excluding components A, B, C, and optional components described later. Specifically, the content of component D in the cleaning composition of the present disclosure is 60% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more, from the viewpoints of improving resin mask peelability, suppressing damage to the passivation film, reducing the wastewater treatment load, and reducing the effect on the substrate, and from the viewpoint of improving resin mask peelability, it is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less. More specifically, the content of component C during use of the cleaning composition of the present disclosure is preferably 60% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 98% by mass or less, and even more preferably 80% by mass or more and 97% by mass or less.
本開示において「洗浄剤組成物中の各成分の含有量」とは、洗浄時、すなわち、洗浄剤組成物の洗浄への使用を開始する時点での各成分の含有量をいう。 In this disclosure, "the content of each component in the cleaning composition" refers to the content of each component at the time of cleaning, i.e., at the time when the cleaning composition starts to be used for cleaning.
（成分Ｅ：界面活性剤）
本開示の洗浄剤組成物は、一又は複数の実施形態において、樹脂マスク剥離性向上、及び、パッシベーション膜へのダメージ抑制の観点から、下記式（ＩＩ）で表される界面活性剤（以下、「成分Ｅ」ともいう）をさらに含有すること好ましい。成分Ｅは、１種でもよいし、２種以上の組合せでもよい。
Ｒ－Ｏ－（ＥＯ）n－Ｈ （ＩＩ）
(Component E: Surfactant)
In one or more embodiments, the cleaning composition of the present disclosure preferably further contains a surfactant represented by the following formula (II) (hereinafter also referred to as "component E") from the viewpoints of improving resin mask strippability and suppressing damage to the passivation film. Component E may be one type or a combination of two or more types.
R-O-(EO) n -H (II)
式（ＩＩ）中、Ｒは炭素数８以上２２以下の炭化水素基を示し、ＥＯはエチレンオキシ基を示し、ｎはＥＯの平均付加モル数であって１２以上３５以下の数である。
式（ＩＩ）において、Ｒは、樹脂マスク剥離性向上、及び、パッシベーション膜へのダメージ抑制の観点から、炭素数８以上２２以下の炭化水素基であり、炭素数１０以上２０以下の直鎖又は分岐鎖のアルキル基及び炭素数１０以上１６以下の直鎖又は分岐鎖のアルケニル基から選ばれる少なくとも１種が好ましく、炭素数１０以上１６以下の直鎖又は分岐鎖のアルキル基がより好ましい。Ｒは、樹脂マスクの剥離性及びパッシベーション膜へのダメージ抑制の観点から、芳香環を有さない炭素数８以上２２以下の炭化水素基であることが好ましい。
Ｒ基の炭素数は、樹脂マスク剥離性向上、及び、パッシベーション膜へのダメージ抑制の観点から、好ましくは８以上、より好ましくは１０以上、更に好ましくは１２以上であり、そして、好ましくは２２以下、より好ましくは２０以下、更に好ましくは１６以下である。すなわち、Ｒ基の炭素数は、好ましくは８以上２２以下、より好ましくは１０以上２０以下、更に好ましくは１２以上１６以下である。Ｒ基の具体例としては、オクチル基、２－エチルヘキシル基、デシル基、イソデシル基、２－プロピルヘプチル基、ドデシル基、トリデシル基、テトラデシル基、及び２－オクチルドデシル基から選ばれる少なくも１種が挙げられる。
式（ＩＩ）において、ｎは、樹脂マスク剥離性向上、及び、パッシベーション膜へのダメージ抑制の観点から、１２以上であって、好ましくは１６以上、より好ましくは２０以上、更に好ましくは２２以上であり、そして、同様の観点から、３５以下であって、好ましくは３０以下、より好ましくは２８以下、更に好ましくは２６以下である。すなわち、ｎは、１２以上３５以下であって、好ましくは１６以上３０以下、より好ましくは２０以上２８以下、更に好ましくは２２以上２６以下である。
In formula (II), R represents a hydrocarbon group having 8 to 22 carbon atoms, EO represents an ethyleneoxy group, and n represents the average number of moles of EO added, which is a number of 12 to 35.
In formula (II), from the viewpoints of improving the peelability of the resin mask and suppressing damage to the passivation film, R is a hydrocarbon group having from 8 to 22 carbon atoms, and is preferably at least one selected from a linear or branched alkyl group having from 10 to 20 carbon atoms and a linear or branched alkenyl group having from 10 to 16 carbon atoms, and more preferably a linear or branched alkyl group having from 10 to 16 carbon atoms. From the viewpoints of improving the peelability of the resin mask and suppressing damage to the passivation film, R is preferably a hydrocarbon group having from 8 to 22 carbon atoms without an aromatic ring.
From the viewpoints of improving the peelability of the resin mask and suppressing damage to the passivation film, the number of carbon atoms in the R group is preferably 8 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 22 or less, more preferably 20 or less, and even more preferably 16 or less. That is, the number of carbon atoms in the R group is preferably 8 or more and 22 or less, more preferably 10 or more and 20 or less, and even more preferably 12 or more and 16 or less. Specific examples of the R group include at least one selected from an octyl group, a 2-ethylhexyl group, a decyl group, an isodecyl group, a 2-propylheptyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a 2-octyldodecyl group.
In formula (II), from the viewpoints of improving the peelability of the resin mask and suppressing damage to the passivation film, n is 12 or more, preferably 16 or more, more preferably 20 or more, and even more preferably 22 or more, and from the same viewpoints, n is 35 or less, preferably 30 or less, more preferably 28 or less, and even more preferably 26 or less. That is, n is 12 or more and 35 or less, preferably 16 or more and 30 or less, more preferably 20 or more and 28 or less, and even more preferably 22 or more and 26 or less.
成分Ｅとしては、例えば、ポリオキシエチレン（２３）ラウリルエーテル、ポリオキシエチレン（２０）２－オクチルドデシルエーテル、及びポリオキシエチレン（１８）アルキル（アルキル基の炭素数１１～１３）エーテルから選ばれる少なくとも１種が挙げられる。（ ）内の数値は平均付加モル数を表わす。 Component E may be, for example, at least one selected from polyoxyethylene (23) lauryl ether, polyoxyethylene (20) 2-octyldodecyl ether, and polyoxyethylene (18) alkyl (alkyl group has 11 to 13 carbon atoms) ether. The numbers in parentheses indicate the average number of moles added.
本開示の洗浄剤組成物が成分Ｅを含む場合、本開示の洗浄剤組成物中の成分Ｅの含有量は、樹脂マスク剥離性向上、及び、パッシベーション膜へのダメージ抑制の観点から、０．１質量％以上が好ましく、０．２質量％以上がより好ましく、０．３質量％以上が更に好ましく、そして、同様の観点から、５質量％以下が好ましく、２質量％以下がより好ましく、０．５質量％以下が更に好ましい。より具体的には、本開示の洗浄剤組成物中の成分Ｅの含有量は、０．１質量％以上５質量％以下が好ましく、０．２質量％以上２質量％以下がより好ましく、０．３質量％以上０．５質量％以下が更に好ましい。成分Ｅが２種以上の組合せである場合、成分Ｅの含有量はそれらの合計含有量をいう。 When the cleaning composition of the present disclosure contains component E, the content of component E in the cleaning composition of the present disclosure is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, from the viewpoints of improving the peelability of the resin mask and suppressing damage to the passivation film, and from the same viewpoint, it is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 0.5% by mass or less. More specifically, the content of component E in the cleaning composition of the present disclosure is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.2% by mass or more and 2% by mass or less, and even more preferably 0.3% by mass or more and 0.5% by mass or less. When component E is a combination of two or more types, the content of component E refers to the total content thereof.
本開示の洗浄剤組成物中の成分Ａの含有量に対する成分Ｅの含有量の質量比（Ｅ／Ａ）は、樹脂マスク剥離性向上、及び、パッシベーション膜へのダメージ抑制の観点から、０．１以上が好ましく、そして、同様の観点から、２以下が好ましく、１以下がより好ましく、０．５以下が更に好ましく、０.３以下が更に好ましく、０.２以下が更に好ましい。より具体的には、質量比（Ｅ／Ａ）は、０．１以上２以下が好ましく、０．１以上１以下がより好ましく、０．１以上０．５以下が更に好ましく、０．１以上０.３以下が更に好ましく、０.１以上０.２以下が更に好ましい。 The mass ratio (E/A) of the content of component E to the content of component A in the cleaning composition of the present disclosure is preferably 0.1 or more from the viewpoint of improving the peelability of the resin mask and suppressing damage to the passivation film, and from the same viewpoint, is preferably 2 or less, more preferably 1 or less, even more preferably 0.5 or less, even more preferably 0.3 or less, and even more preferably 0.2 or less. More specifically, the mass ratio (E/A) is preferably 0.1 or more and 2 or less, more preferably 0.1 or more and 1 or less, even more preferably 0.1 or more and 0.5 or less, even more preferably 0.1 or more and 0.3 or less, and even more preferably 0.1 or more and 0.2 or less.
（成分Ｆ：有機溶媒）
本開示の洗浄剤組成物は、一又は複数の実施形態において、有機溶媒（以下、「成分Ｆ」ともいう）をさらに含んでもよい。成分Ｆは、１種でもよいし、２種以上の組合せでもよい。
成分Ｆとしては、例えば、１－メチル－２－ピロリドン（ＮＭＰ）、ジメチルスルホキシド、イソホロン、ベンジルアルコール、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ブチルエーテル等が挙げられる。
本開示の洗浄剤組成物が成分Ｆを含む場合、本開示の洗浄剤組成物中の成分Ｆの含有量は、樹脂マスク剥離性向上、パッシベーション膜へのダメージ抑制、排水処理負荷低減、及び基板に対する影響低減の観点から、１０質量％未満が好ましく、８質量％以下がより好ましく、６質量％以下が更に好ましく、そして、樹脂マスク剥離性向上の観点から、２質量％以上が好ましく、３質量％以上がより好ましく、４質量％以上が更に好ましい。より具体的には、本開示の洗浄剤組成物中の成分Ｆの含有量は、２質量％以上１０質量％未満が好ましく、３質量％以上８質量％以下がより好ましく、４質量％以上６質量％以下が更に好ましい。成分Ｆが２種以上の組合せである場合、成分Ｆの含有量はそれらの合計含有量をいう。
本開示の洗浄剤組成物中における水（成分Ｄ）と有機溶媒（成分Ｆ）との質量比（Ｄ／Ｆ）は、樹脂マスク剥離性向上、パッシベーション膜へのダメージ抑制、排水処理負荷低減、及び基板に対する影響低減の観点から、１００／０～８０／２０が好ましく、１００／０～９０／１０がより好ましく、１００／０～９５／５が更に好ましい。
(Component F: Organic Solvent)
In one or more embodiments, the cleaning composition of the present disclosure may further include an organic solvent (hereinafter, also referred to as "component F"). Component F may be one type or a combination of two or more types.
Examples of component F include 1-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, isophorone, benzyl alcohol, diethylene glycol monobutyl ether, and diethylene glycol dibutyl ether.
When the cleaning composition of the present disclosure contains component F, the content of component F in the cleaning composition of the present disclosure is preferably less than 10% by mass, more preferably 8% by mass or less, and even more preferably 6% by mass or less from the viewpoints of improving resin mask peelability, suppressing damage to the passivation film, reducing the load on wastewater treatment, and reducing the effect on the substrate, and from the viewpoint of improving resin mask peelability, it is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 4% by mass or more. More specifically, the content of component F in the cleaning composition of the present disclosure is preferably 2% by mass or more and less than 10% by mass, more preferably 3% by mass or more and 8% by mass or less, and even more preferably 4% by mass or more and 6% by mass or less. When component F is a combination of two or more kinds, the content of component F refers to the total content thereof.
The mass ratio (D/F) of water (component D) to the organic solvent (component F) in the cleaning composition of the present disclosure is preferably 100/0 to 80/20, more preferably 100/0 to 90/10, and even more preferably 100/0 to 95/5, from the viewpoints of improving resin mask peelability, suppressing damage to a passivation film, reducing the load of wastewater treatment, and reducing the effect on a substrate.
（その他の成分）
本開示の洗浄剤組成物は、前記成分Ａ～Ｆ以外に、必要に応じてその他の成分をさらに含有することができる。その他の成分としては、通常の洗浄剤に用いられうる成分を挙げることができ、例えば、成分Ａ～Ｃ以外のアルカリ剤、成分Ｅ以外の界面活性剤、キレート剤、増粘剤、分散剤、防錆剤、高分子化合物、可溶化剤、酸化防止剤、防腐剤、消泡剤、抗菌剤等が挙げられる。
本開示の洗浄剤組成物がその他の成分を含む場合、本開示の洗浄剤組成物中のその他の含有量は、０質量％以上２質量％以下が好ましく、０質量％以上１．５質量％以下がより好ましく、０質量％以上１．３質量％以下が更に好ましく、０質量％以上１質量％以下がより更に好ましい。
(Other ingredients)
The cleaning agent composition of the present disclosure may further contain other components as necessary in addition to the above-described Components A to F. Examples of other components include components that can be used in ordinary cleaning agents, such as alkaline agents other than Components A to C, surfactants other than Component E, chelating agents, thickening agents, dispersants, rust inhibitors, polymeric compounds, solubilizing agents, antioxidants, preservatives, defoamers, antibacterial agents, etc.
When the cleaning agent composition of the present disclosure contains other components, the content of the other components in the cleaning agent composition of the present disclosure is preferably from 0 mass% to 2 mass%, more preferably from 0 mass% to 1.5 mass%, even more preferably from 0 mass% to 1.3 mass%, and still more preferably from 0 mass% to 1 mass%.
本開示の洗浄剤組成物は、一又は複数の実施形態において、有機溶剤、成分Ｃ以外のアルカリ金属塩、防食剤、脂肪族アミン、酸性有機化合物、オクチル酸、フッ化合物、成分Ｂ以外のオキソアンモニウム化合物、酸化剤、ポリアクリル酸、アセトニトリル、過酸化物、第４級アンモニウム塩の過酸化水素化物、及び、アルキルジフェニルエーテルジスルフォン酸塩から選ばれる少なくとも１種の成分を含まないものとすることができる。 In one or more embodiments, the cleaning composition of the present disclosure may be free of at least one component selected from organic solvents, alkali metal salts other than component C, anticorrosive agents, aliphatic amines, acidic organic compounds, octylic acid, fluorine compounds, oxoammonium compounds other than component B, oxidizing agents, polyacrylic acid, acetonitrile, peroxides, hydrogen peroxides of quaternary ammonium salts, and alkyl diphenyl ether disulfonates.
本開示の洗浄剤組成物の使用時における成分Ａ及び任意成分（成分Ｅ、成分Ｆ、その他の成分）由来の有機物の総含有量は、排水処理負荷低減、及び基板に対する影響低減の観点から、３０質量％以下が好ましく、２５質量％以下がより好ましく、２０質量％以下が更に好ましく、１６質量％以下がより更に好ましく、そして、樹脂マスク剥離性向上の観点から、２質量％以上が好ましく、３質量％以上がより好ましく、４質量％以上が更に好ましく、６質量％以上がより更に好ましい。より具体的には、本開示の洗浄剤組成物の使用時における成分Ａ及び任意成分（成分Ｅ、成分Ｆ、その他の成分）由来の有機物の総含有量は、２質量％以上３０質量％以下が好ましく、３質量％以上２５質量％以下がより好ましく、４質量％以上２０質量％以下が更に好ましく、６質量％以上１６質量％以下がより更に好ましい。 The total content of organic matter derived from component A and optional components (component E, component F, other components) during use of the cleaning composition of the present disclosure is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and even more preferably 16% by mass or less, from the viewpoint of reducing the wastewater treatment load and reducing the impact on the substrate, and is preferably 2% by mass or more, more preferably 3% by mass or more, even more preferably 4% by mass or more, and even more preferably 6% by mass or more, from the viewpoint of improving the peelability of the resin mask. More specifically, the total content of organic matter derived from component A and optional components (component E, component F, other components) during use of the cleaning composition of the present disclosure is preferably 2% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, even more preferably 4% by mass or more and 20% by mass or less, and even more preferably 6% by mass or more and 16% by mass or less.
（洗浄剤組成物のｐＨ）
本開示の洗浄剤組成物のｐＨは、樹脂マスク剥離性向上、及び、パッシベーション膜へのダメージ抑制、及び、基板に対する影響低減の観点から、１１以上が好ましく、１２以上がより好ましく、１３以上が更に好ましく、そして、１４以下が好ましく、１３．８以下がより好ましい。ｐＨは、必要により、硝酸、硫酸等の無機酸、オキシカルボン酸、多価カルボン酸、アミノポリカルボン酸、アミノ酸等の有機酸、及びそれらの金属塩やアンモニウム塩、アルカリ剤等を用いて調整することができる。本開示において洗浄剤組成物のｐＨは、２５℃における洗浄剤組成物の使用時のｐＨであり、ｐＨメータを用いて測定できる。具体的には、実施例に記載の方法により測定できる。
(pH of cleaning composition)
The pH of the cleaning composition of the present disclosure is preferably 11 or more, more preferably 12 or more, even more preferably 13 or more, and preferably 14 or less, more preferably 13.8 or less, from the viewpoints of improving the peelability of the resin mask, suppressing damage to the passivation film, and reducing the influence on the substrate. If necessary, the pH can be adjusted using an inorganic acid such as nitric acid or sulfuric acid, an organic acid such as an oxycarboxylic acid, a polycarboxylic acid, an aminopolycarboxylic acid, or an amino acid, and their metal salts, ammonium salts, an alkali agent, or the like. In the present disclosure, the pH of the cleaning composition is the pH at 25° C. when the cleaning composition is used, and can be measured using a pH meter. Specifically, it can be measured by the method described in the Examples.
（洗浄剤組成物の製造方法）
本開示の洗浄剤組成物は、一又は複数の実施形態において、成分Ａ、成分Ｂ、及びＣ、成分Ｄ及び必要に応じて上述した任意成分（成分Ｅ、成分Ｆ、その他の成分）を公知の方法で配合することにより製造できる。例えば、本開示の洗浄剤組成物は、一又は複数の実施形態において、成分Ａ、成分Ｂ、成分Ｃ及び成分Ｄを配合してなるものとすることができる。
したがって、本開示は、少なくとも成分Ａ、成分Ｂ、成分Ｃ及び成分Ｄを配合する工程を含む、洗浄剤組成物の製造方法に関する。本開示において「配合する」とは、成分Ａ、成分Ｂ、成分Ｃ、成分Ｄ及び必要に応じて上述した任意成分（成分Ｅ、成分Ｆ、その他の成分）を同時に又は任意の順に混合することを含む。本開示の洗浄剤組成物の製造方法において、各成分の好ましい配合量は、上述した本開示の洗浄剤組成物の各成分の好ましい含有量と同じとすることができる。
(Method for producing the cleaning composition)
In one or more embodiments, the cleaning composition of the present disclosure can be produced by blending components A, B, C, and D, and the optional components described above (component E, component F, and other components) as necessary, by a known method. For example, in one or more embodiments, the cleaning composition of the present disclosure can be produced by blending components A, B, C, and D.
Thus, the present disclosure relates to a method for producing a cleaning composition, the method including a step of blending at least Component A, Component B, Component C, and Component D. In the present disclosure, "blending" includes mixing Component A, Component B, Component C, Component D, and the above-mentioned optional components (Component E, Component F, and other components) simultaneously or in any order as necessary. In the method for producing a cleaning composition of the present disclosure, the preferred blending amount of each component may be the same as the preferred content of each component in the cleaning composition of the present disclosure described above.
本開示の洗浄剤組成物は、そのまま洗浄に使用する形態であってもよく、分離や析出等を起こして保管安定性を損なわない範囲で水（成分Ｄ）の量を減らした濃縮物として調製してもよい。洗浄剤組成物の濃縮物は、輸送及び貯蔵の観点から、希釈倍率３倍以上の濃縮物とすることが好ましく、保管安定性の観点から、希釈倍率３０倍以下の濃縮物とすることが好ましい。洗浄剤組成物の濃縮物は、使用時に各成分（成分Ａ、成分Ｂ、成分Ｃ、成分Ｄ、成分Ｅ、成分Ｆ及びその他の成分）が上述した含有量（すなわち、洗浄時の含有量）になるよう水（成分Ｄ）で希釈して使用することができる。更に洗浄剤組成物の濃縮物は、使用時に各成分を別々に添加して使用することもできる。本開示において濃縮液の洗浄剤組成物の「使用時」又は「洗浄時」とは、洗浄剤組成物の濃縮物が希釈された状態をいう。 The cleaning composition of the present disclosure may be in a form used for cleaning as it is, or may be prepared as a concentrate in which the amount of water (component D) is reduced to the extent that separation, precipitation, etc. do not occur and storage stability is not impaired. The concentrate of the cleaning composition is preferably a concentrate diluted 3 times or more from the viewpoint of transportation and storage, and is preferably a concentrate diluted 30 times or less from the viewpoint of storage stability. The concentrate of the cleaning composition can be used by diluting it with water (component D) so that each component (component A, component B, component C, component D, component E, component F, and other components) has the above-mentioned content (i.e., content at the time of cleaning) at the time of use. Furthermore, the concentrate of the cleaning composition can also be used by adding each component separately at the time of use. In the present disclosure, "at the time of use" or "at the time of cleaning" of the concentrated cleaning composition refers to the state in which the concentrate of the cleaning composition is diluted.
［電子部品の製造方法］
本開示は、一態様において、本開示の剥離方法を用いて、樹脂マスクを有する基板（被洗浄物）から樹脂マスクを剥離する工程（剥離工程）を含む、電子部品の製造方法（以下、「本開示の電子部品の製造方法」ともいう）に関する。被洗浄物としては、上述した被洗浄物を挙げることができる。
本開示の電子部品の製造方法によれば、電子部品に付着した樹脂マスクを効果的に剥離できるため、信頼性の高い電子部品の製造が可能になる。更に、本開示の洗浄方法を行うことにより、電子部品に付着した樹脂マスクの剥離が容易になることから、洗浄時間が短縮化でき、電子部品の製造効率を向上できる。
[Electronic component manufacturing method]
In one aspect, the present disclosure relates to a method for producing an electronic component (hereinafter also referred to as the "method for producing an electronic component of the present disclosure"), which includes a step (peeling step) of peeling a resin mask from a substrate (object to be cleaned) having the resin mask thereon by using the peeling method of the present disclosure. Examples of the object to be cleaned include the above-mentioned objects to be cleaned.
According to the manufacturing method of electronic components of the present disclosure, the resin mask attached to the electronic components can be effectively peeled off, which enables the manufacturing of highly reliable electronic components. Furthermore, by carrying out the cleaning method of the present disclosure, the resin mask attached to the electronic components can be easily peeled off, which shortens the cleaning time and improves the manufacturing efficiency of electronic components.
本開示の電子部品の製造方法は、一又は複数の実施形態において、下記工程（１）～（５）を含むことができる。
（１）基板上に配線を形成する工程（配線形成工程）
（２）配線が形成された基板にパッシベーション膜を形成する工程（パッシベーション膜形成工程）
（３）パッシベーション膜上にレジストを塗布し、レジストを露光及び／又は現像処理し、パターン化されたレジスト膜を形成する工程（レジスト膜形成工程）
（４）パターン化されたレジスト膜をマスクとしためっき、現像、エッチングなどの各種加工工程（加工工程）
（５）本開示の洗浄剤組成物を用いてレジスト膜（樹脂マスク）を剥離する工程（剥離工程）
In one or more embodiments, the method for producing an electronic component according to the present disclosure may include the following steps (1) to (5).
(1) A process for forming wiring on a substrate (a wiring forming process)
(2) A step of forming a passivation film on the substrate on which the wiring has been formed (passivation film forming step)
(3) A process of applying a resist onto the passivation film, exposing and/or developing the resist, and forming a patterned resist film (resist film forming process).
(4) Various processing steps such as plating, developing, and etching using a patterned resist film as a mask (processing steps)
(5) A step of stripping a resist film (resin mask) using the cleaning composition of the present disclosure (stripping step).
［キット］
本開示は、一態様において、本開示の剥離方法及び本開示の電子部品の製造方法のいずれかに使用するためのキット（以下、「本開示のキット」ともいう）に関する。本開示のキットは、一又は複数の実施形態において、本開示の洗浄剤組成物を製造するためのキットである。本開示のキットによれば、樹脂マスク剥離性に優れる洗浄剤組成物を得ることができる。
[kit]
In one aspect, the present disclosure relates to a kit for use in any one of the stripping method of the present disclosure and the method for producing an electronic component of the present disclosure (hereinafter, also referred to as the "kit of the present disclosure"). In one or more embodiments, the kit of the present disclosure is a kit for producing the cleaning composition of the present disclosure. According to the kit of the present disclosure, a cleaning composition having excellent resin mask stripping properties can be obtained.
本開示のキットとしては、一又は複数の実施形態において、第１液と第２液とを相互に混合されない状態で含み、成分Ａ、成分Ｂ及び成分Ｃがそれぞれ、第１液及び第２液のうちのいずれか一方又は双方に含まれており、使用時に第１液と第２液とが混合されるキット（２液型洗浄剤組成物）が挙げられる。第１液と第２液とが混合された後、必要に応じて水（成分Ｄ）を用いて希釈されてもよい。第１液及び第２液にはそれぞれ必要に応じて、上述した任意成分（成分Ｅ、成分Ｆ、その他の成分）が含まれていてもよい。
本開示のキットとしては、一又は複数の実施形態において、成分Ａ及び成分Ｂを含有する溶液（第１ａ液）と、成分Ｃを含有する溶液（第２ａ液）とを、相互に混合されない状態で含み、第１ａ液及び第２ａ液の少なくとも１つは、水（成分Ｄ）の一部又は全部を更に含有し、第１ａ液と第２ａ液とは使用時に混合されるキット（２液型洗浄剤組成物）が挙げられる。第１ａ液と第２ａ液とが混合された後、必要に応じて水（成分Ｄ）で希釈されてもよい。第１ａ液及び第２ａ液の各々には、必要に応じて上述した任意成分（成分Ｅ、成分Ｆ、その他の成分）が含まれていてもよい。
In one or more embodiments, the kit of the present disclosure includes a kit (two-liquid cleaning agent composition) that contains the first liquid and the second liquid in a mutually unmixed state, and that contains components A, B, and C in either or both of the first liquid and the second liquid, and that mixes the first liquid and the second liquid when used. After the first liquid and the second liquid are mixed, they may be diluted with water (component D) as necessary. The first liquid and the second liquid may each contain the above-mentioned optional components (component E, component F, other components) as necessary.
In one or more embodiments, the kit of the present disclosure includes a kit (two-liquid cleaning agent composition) that includes a solution (Liquid 1a) containing Component A and Component B and a solution (Liquid 2a) containing Component C in a mutually unmixed state, at least one of Liquid 1a and Liquid 2a further contains a part or all of water (Component D), and Liquid 1a and Liquid 2a are mixed at the time of use. After Liquid 1a and Liquid 2a are mixed, they may be diluted with water (Component D) as necessary. Each of Liquid 1a and Liquid 2a may contain the above-mentioned optional components (Component E, Component F, other components) as necessary.
以下に、実施例により本開示を具体的に説明するが、本開示はこれらの実施例によって何ら限定されるものではない。 The present disclosure will be explained in detail below with reference to examples, but the present disclosure is not limited to these examples.
１．実施例１～１４及び比較例１～４の洗浄剤組成物の調製
表１～３に示す各成分を表１～３に記載の配合量（質量％、有効分）で配合し、それを攪拌して混合することにより、実施例１～１４及び比較例１～４の洗浄剤組成物を調製した。
1. Preparation of cleaning agent compositions of Examples 1 to 14 and Comparative Examples 1 to 4 The components shown in Tables 1 to 3 were blended in the blending amounts (mass %, active content) shown in Tables 1 to 3 and mixed by stirring to prepare cleaning agent compositions of Examples 1 to 14 and Comparative Examples 1 to 4.
実施例１～１４及び比較例１～４の洗浄剤組成物の調製には、下記のものを使用した。
（成分Ａ）
テトラメチルアンモニウムヒドロキシド［昭和電工株式会社製、濃度２５％］
（成分Ｂ）
ヒドロキシルアミン［富士フィルム和光純薬株式会社製］
（成分Ｃ）
ＫＯＨ：水酸化カリウム［富士フィルム和光純薬株式会社製］
（非成分Ｃ）
ＮａＯＨ：水酸化ナトリウム［南海化学株式会社製］
（成分Ｄ）
水［オルガノ株式会社製純水装置G-10DSTSETで製造した1μS/ｃｍ以下の純水］
（成分Ｅ）
ポリオキシエチレン（１８）アルキルエーテル［花王株式会社製］（式（ＩＩ）中のＲ：炭素数１１～１３のアルキル基、ｎ：１８、）
ポリオキシエチレン（２３）ラウリルエーテル［花王株式会社製］［式（ＩＩ）中のＲ：炭素数１２のアルキル基、ｎ：２３］
（非成分Ｅ）
ポリオキシエチレン（６）ラウリルエーテル［花王株式会社製］（式（ＩＩ）中のＲ：炭素数１２のアルキル基、ｎ：６）
（成分Ｆ）
ＮＭＰ：１－メチル－２－ピロリドン［富士フイルム和光純薬株式会社製］
The following materials were used to prepare the cleaning compositions of Examples 1 to 14 and Comparative Examples 1 to 4.
(Component A)
Tetramethylammonium hydroxide [Showa Denko K.K., concentration 25%]
(Component B)
Hydroxylamine [Fujifilm Wako Pure Chemical Industries, Ltd.]
(Component C)
KOH: Potassium hydroxide [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
(Non-Component C)
NaOH: Sodium hydroxide [manufactured by Nankai Chemical Co., Ltd.]
(Component D)
Water [Pure water of 1 μS/cm or less produced using the Organo Corporation pure water system G-10DSTSET]
(Component E)
Polyoxyethylene (18) alkyl ether [manufactured by Kao Corporation] (R in formula (II): alkyl group having 11 to 13 carbon atoms, n: 18)
Polyoxyethylene (23) lauryl ether [manufactured by Kao Corporation] [R in formula (II): alkyl group having 12 carbon atoms, n: 23]
(Non-Component E)
Polyoxyethylene (6) lauryl ether [manufactured by Kao Corporation] (R in formula (II): alkyl group having 12 carbon atoms, n: 6)
(Component F)
NMP: 1-methyl-2-pyrrolidone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
２．洗浄剤組成物のｐＨの測定方法
洗浄剤組成物の２５℃におけるｐＨは、ｐＨメータ（東亜電波工業株式会社、ＨＭ－３０Ｇ）を用いて測定した値であり、ｐＨメータの電極を洗浄剤組成物に浸漬して３分後の数値である。
2. Method for measuring pH of cleaning composition The pH of the cleaning composition at 25° C. was measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G) and was the value 3 minutes after immersing the electrodes of the pH meter in the cleaning composition.
３．実施例１～１４及び比較例１～４の洗浄剤組成物の評価
調製した実施例１～１４及び比較例１～４の洗浄剤組成物について下記評価を行った。
3. Evaluation of the cleaning compositions of Examples 1 to 14 and Comparative Examples 1 to 4 The cleaning compositions prepared in Examples 1 to 14 and Comparative Examples 1 to 4 were evaluated as follows.
［樹脂マスクを有するテストピースの作製］
ＰＫＧ（半導体パッケージ）基板回路形成用感光性フィルム（ネガ型レジストフィルム、アクリル酸ポリマー含有タイプ）を無電解めっき後の基板表面に下記条件でラミネートし、選択的に露光処理して露光部を硬化した後（露光工程）、現像処理することで未露光部を除去し（現像工程）、樹脂マスク（硬化したレジスト膜：アクリル酸系ポリマー膜、厚さ２４０μｍ、ピラーピッチ２００μｍ）のパターンを有する基板を得た。そして、前記現像処理で未露光部が除去された領域を銅めっき処理（厚さ２３０μｍ）することで、表面に銅含有金属層（ピラー）及び硬化したレジスト層である樹脂マスクを有する基板からなるテストピース（テストピース、３０ｍｍ×３０ｍｍ）を得た。
（１）ラミネート：クリーンローラー（株式会社レヨーン工業製、ＲＹ－５０５Ｚ）及び真空アプリケータ（ローム＆ハース社製、ＶＡ７０２４／ＨＰ５）を用いてローラー温度５０℃、ローラー圧１．４Ｂａｒで行う。
（２）露光：プリント基板用直接描画装置（株式会社ＳＣＲＥＥＮグラフィックアンドプレシジョンソリューションズ製、Ｍｅｒｃｕｒｅｘ ＬＩ－９５００）を用い、露光量１５ｍＪ／ｃｍ2で露光を行う。
（３）パターン形状：ピラー径１００μｍ、ピッチ２００μｍ
（４）現像：基板用現像装置（揚博科技株式会社製、ＬＴ－９８０３６６）、３０℃の１％炭酸ナトリウム水溶液を用いて、スプレー圧０．２ＭＰａ、未露光部の樹脂マスクを除去する。
［パッシベーション膜を有するテストピースの作製］
ポリベンゾオキサゾール（ＰＢＯ）前駆体をスピンコート法によってウエハに成膜し、パターニング後に熱処理して硬化した。続いてダイシングを行うことでパッシベーション膜（ＰＢＯ膜、厚さ１０μｍ）を有するテストピース（１０ｍｍ×１０ｍｍ）を得た。
[Preparation of test pieces having resin masks]
A photosensitive film for forming a circuit board for PKG (semiconductor package) (negative resist film, acrylic acid polymer-containing type) was laminated on the surface of the substrate after electroless plating under the following conditions, selectively exposed to light to harden the exposed parts (exposure process), and then developed to remove the unexposed parts (development process), to obtain a substrate having a pattern of a resin mask (hardened resist film: acrylic acid-based polymer film, thickness 240 μm, pillar pitch 200 μm). The region from which the unexposed parts were removed in the development process was copper-plated (thickness 230 μm), to obtain a test piece (test piece, 30 mm x 30 mm) consisting of a substrate having a copper-containing metal layer (pillar) and a resin mask that is a hardened resist layer on the surface.
(1) Lamination: Using a clean roller (RY-505Z, manufactured by Rayon Kogyo Co., Ltd.) and a vacuum applicator (VA7024/HP5, manufactured by Rohm and Haas Co.), the roller temperature was 50° C. and the roller pressure was 1.4 Bar.
(2) Exposure: Exposure is performed using a direct imaging device for printed circuit boards (Mercurex LI-9500, manufactured by SCREEN Graphic and Precision Solutions Co., Ltd.) at an exposure dose of 15 mJ/cm 2 .
(3) Pattern shape: pillar diameter 100 μm, pitch 200 μm
(4) Development: Using a substrate developing device (LT-980366, manufactured by Yangbo Technology Co., Ltd.), a 1% aqueous sodium carbonate solution at 30° C. is used, and the resin mask of the unexposed area is removed at a spray pressure of 0.2 MPa.
[Preparation of test pieces having passivation films]
A polybenzoxazole (PBO) precursor was formed on a wafer by spin coating, patterned, and then heat-treated to harden it.Then, a test piece (10 mm x 10 mm) having a passivation film (PBO film, thickness 10 μm) was obtained by dicing.
［樹脂マスクの剥離性の評価］
トール型の２００ｍＬガラスビーカーに、実施例１～１４及び比較例１～４の各洗浄剤組成物を１００ｇ添加して６０℃に加温し、回転子（フッ素樹脂（ＰＴＦＥ）、φ８ｍｍ×２５ｍｍ）を用いて回転数３００ｒｐｍで撹拌した状態で、樹脂マスク（厚さ２４０μｍ）を有するテストピースを浸漬する。そして樹脂マスクが剥離されるまで浸漬開始から４５分後、９０分後、１２０分後及び１３５分後に樹脂マスクの剥離状況を観察し、以下の基準にて評価を行った。結果を表１～３に示した。
＜評価基準＞
Ａ：４５分以内に樹脂マスクの剥離が進行し、残渣が見られなくなる。
Ｂ：４５分超９０分以内に樹脂マスクの剥離が進行し、残渣が見られなくなる。
Ｃ：９０分超１２０分以内に樹脂マスクの剥離が進行し、残渣が見られなくなる。
Ｄ：１２０分超１３５分以内に樹脂マスクの剥離が進行し、残渣が見られなくなる。
Ｅ：１３５分超でも剥離残渣が見られる。
[Evaluation of Resin Mask Peelability]
100 g of each of the cleaning compositions of Examples 1 to 14 and Comparative Examples 1 to 4 was added to a tall 200 mL glass beaker and heated to 60° C. The test piece having a resin mask (thickness 240 μm) was immersed in the mixture while stirring at 300 rpm using a rotor (fluororesin (PTFE), φ8 mm × 25 mm). The peeling state of the resin mask was observed 45 minutes, 90 minutes, 120 minutes, and 135 minutes after the start of immersion until the resin mask was peeled off, and evaluation was performed according to the following criteria. The results are shown in Tables 1 to 3.
<Evaluation criteria>
A: Peeling of the resin mask progresses within 45 minutes, and no residue is observed.
B: Peeling of the resin mask progresses from more than 45 minutes to within 90 minutes, and no residue is observed.
C: Peeling of the resin mask progresses from more than 90 minutes to within 120 minutes, and no residue is observed.
D: Peeling of the resin mask progresses between more than 120 minutes and 135 minutes, and no residue is observed.
E: Peeling residue is observed even after 135 minutes.
［パッシベーション膜へのダメージの評価］
トール型の２００ｍＬガラスビーカーに、実施例１０～１２の各洗浄剤組成物を１００ｇ添加して６０℃に加温した状態で、パッシベーション膜（ＰＢＯ膜、厚さ１０μｍ）を有するテストピースを６０分間浸漬する。そして、１００ｍＬガラスビーカーに水を１００ｇ添加したすすぎ槽へ浸漬してすすいだ後、窒素ブローにて乾燥する。パッシベーション膜の形状変化を目視で観察し、以下の基準にて評価を行った。結果を表２に示した。
＜評価基準＞
Ａ：変化が見られない。
Ｂ：変化（しわ、欠落など）が見られる。
[Evaluation of damage to passivation film]
100 g of each of the cleaning compositions of Examples 10 to 12 was added to a tall 200 mL glass beaker and heated to 60° C. In this state, a test piece having a passivation film (PBO film, thickness 10 μm) was immersed for 60 minutes. The test piece was then immersed in a rinsing tank containing 100 g of water in a 100 mL glass beaker, rinsed, and then dried by nitrogen blowing. The change in shape of the passivation film was visually observed and evaluated according to the following criteria. The results are shown in Table 2.
<Evaluation criteria>
A: No change was observed.
B: Changes (wrinkles, defects, etc.) are observed.
表１に示すとおり、実施例１～９の洗浄剤組成物は、成分Ａを含まない比較例１、成分Ｂを含まない比較例２、成分Ｃを含まない比較例３～４に比べて、厚さ２４０μｍの樹脂マスク剥離性に優れていることが分かった。
表２に示すとおり、界面活性剤として成分Ｅを含む実施例１０～１１の洗浄剤組成物は、界面活性剤として非成分Ｅを含む実施例１２に比べて、パッシベーション膜へのダメージが抑制され、かつ、厚さ２４０μｍの樹脂マスク剥離性に優れていることが分かった。
表３に示すとおり、洗浄剤組成物が有機溶剤（成分Ｆ）を含む場合、質量比Ｄ／Ｆが９１/９である実施例１４は、質量比Ｄ／Ｆが７３/２７である実施例１３に比べて、厚さ２４０μｍの樹脂マスク剥離性に優れていることが分かった。
なお、従来から行われているプリント基板に微細配線を形成に用いられる樹脂マスクの厚さは最大３０μｍ程度である。
As shown in Table 1, the cleaning compositions of Examples 1 to 9 were found to have superior peelability for a resin mask having a thickness of 240 μm compared to Comparative Example 1 not containing Component A, Comparative Example 2 not containing Component B, and Comparative Examples 3 and 4 not containing Component C.
As shown in Table 2, the cleaning compositions of Examples 10 and 11, which contained Component E as a surfactant, caused less damage to the passivation film and were excellent in peeling property of a 240 μm-thick resin mask, compared to Example 12, which contained a non-Component E as a surfactant.
As shown in Table 3, when the cleaning composition contained an organic solvent (component F), Example 14 in which the mass ratio D/F was 91/9 was superior in strippability of a resin mask with a thickness of 240 μm to Example 13 in which the mass ratio D/F was 73/27.
Incidentally, the thickness of the resin mask conventionally used for forming fine wiring on a printed circuit board is about 30 μm at maximum.
本開示によれば、樹脂マスク剥離性に優れる樹脂マスク剥離方法を提供できる。本開示の剥離方法を用いることで、電子部品の性能・信頼性の向上が可能となり、半導体装置の生産性を向上できる。 According to the present disclosure, a resin mask peeling method with excellent resin mask peeling properties can be provided. By using the peeling method of the present disclosure, it is possible to improve the performance and reliability of electronic components, and to improve the productivity of semiconductor devices.
Claims (17)
樹脂マスクの厚さが１００μｍ以上であり、
前記洗浄剤組成物は、下記成分Ａ、下記成分Ｂ、下記成分Ｃ及び下記成分Ｄを含有する水系洗浄剤であり、
前記洗浄剤組成物中の成分Ｄの含有量が、６０質量％以上である、樹脂マスクの剥離方法。
成分Ａ：第４級アンモニウム水酸化物
成分Ｂ：ヒドロキシルアミン
成分Ｃ：水酸化カリウム
成分Ｄ：水 The method includes a step of removing the resin mask from a substrate having the resin mask by using the cleaning composition,
The thickness of the resin mask is 100 μm or more,
The cleaning agent composition is an aqueous cleaning agent containing the following component A, the following component B, the following component C, and the following component D,
The method for removing a resin mask, wherein the content of component D in the cleaning composition is 60 mass% or more.
Component A: Quaternary ammonium hydroxide Component B: Hydroxylamine Component C: Potassium hydroxide Component D: Water
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008072059A (en) | 2006-09-15 | 2008-03-27 | Nec Lcd Technologies Ltd | Chemical and method for treating substrate using the same |
| JP2009206335A (en) | 2008-02-28 | 2009-09-10 | Hayashi Junyaku Kogyo Kk | Silicon anisotropic etching liquid composition |
| JP2011502281A (en) | 2007-10-31 | 2011-01-20 | イー．ケー．シー．テクノロジー．インコーポレーテッド | Photoresist stripping compound |
| WO2011027773A1 (en) | 2009-09-02 | 2011-03-10 | 和光純薬工業株式会社 | Resist remover composition and method for removing resist using the composition |
| WO2011040484A1 (en) | 2009-10-02 | 2011-04-07 | 三菱瓦斯化学株式会社 | Silicon etching solution and etching method |
| JP2013008900A (en) | 2011-06-27 | 2013-01-10 | Fujifilm Corp | Formation method of capacitor structure and silicon etchant for use therein |
| WO2016076034A1 (en) | 2014-11-13 | 2016-05-19 | 三菱瓦斯化学株式会社 | Alkaline earth metal-containing cleaning solution for cleaning semiconductor element, and method for cleaning semiconductor element using same |
| JP2019105670A (en) | 2017-12-08 | 2019-06-27 | 花王株式会社 | Detergent composition for stripping resin mask |
-
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- 2023-01-26 KR KR1020247021944A patent/KR20240144110A/en unknown
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008072059A (en) | 2006-09-15 | 2008-03-27 | Nec Lcd Technologies Ltd | Chemical and method for treating substrate using the same |
| JP2011502281A (en) | 2007-10-31 | 2011-01-20 | イー．ケー．シー．テクノロジー．インコーポレーテッド | Photoresist stripping compound |
| JP2009206335A (en) | 2008-02-28 | 2009-09-10 | Hayashi Junyaku Kogyo Kk | Silicon anisotropic etching liquid composition |
| WO2011027773A1 (en) | 2009-09-02 | 2011-03-10 | 和光純薬工業株式会社 | Resist remover composition and method for removing resist using the composition |
| WO2011040484A1 (en) | 2009-10-02 | 2011-04-07 | 三菱瓦斯化学株式会社 | Silicon etching solution and etching method |
| JP2013008900A (en) | 2011-06-27 | 2013-01-10 | Fujifilm Corp | Formation method of capacitor structure and silicon etchant for use therein |
| WO2016076034A1 (en) | 2014-11-13 | 2016-05-19 | 三菱瓦斯化学株式会社 | Alkaline earth metal-containing cleaning solution for cleaning semiconductor element, and method for cleaning semiconductor element using same |
| JP2019105670A (en) | 2017-12-08 | 2019-06-27 | 花王株式会社 | Detergent composition for stripping resin mask |
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