CN108026491A - 清洁组合物 - Google Patents
清洁组合物 Download PDFInfo
- Publication number
- CN108026491A CN108026491A CN201680044375.5A CN201680044375A CN108026491A CN 108026491 A CN108026491 A CN 108026491A CN 201680044375 A CN201680044375 A CN 201680044375A CN 108026491 A CN108026491 A CN 108026491A
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- polymer film
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- 239000000203 mixture Substances 0.000 title claims abstract description 148
- 238000004140 cleaning Methods 0.000 title claims abstract description 70
- -1 alcohol amine compound Chemical class 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 67
- 238000012545 processing Methods 0.000 claims description 44
- 229920000642 polymer Polymers 0.000 claims description 42
- 229920006254 polymer film Polymers 0.000 claims description 42
- 238000000608 laser ablation Methods 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000004642 Polyimide Substances 0.000 claims description 25
- 229920001721 polyimide Polymers 0.000 claims description 25
- 239000004065 semiconductor Substances 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- 235000012431 wafers Nutrition 0.000 claims description 17
- 239000012634 fragment Substances 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 13
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 12
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- 239000012964 benzotriazole Substances 0.000 claims description 11
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000002679 ablation Methods 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000003852 triazoles Chemical class 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000005418 aryl aryl group Chemical group 0.000 claims description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 125000004415 heterocyclylalkyl group Chemical group 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 4
- 229940043276 diisopropanolamine Drugs 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical class CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 3
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical group CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043237 diethanolamine Drugs 0.000 claims description 3
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 claims description 3
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 3
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Substances [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical class CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical class CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N hydroxylamine hydrochloride Substances Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 2
- XBUFCZMOAHHGMX-UHFFFAOYSA-N hydroxylamine;phosphoric acid Chemical compound ON.ON.ON.OP(O)(O)=O XBUFCZMOAHHGMX-UHFFFAOYSA-N 0.000 claims description 2
- WCYJQVALWQMJGE-UHFFFAOYSA-M hydroxylammonium chloride Chemical compound [Cl-].O[NH3+] WCYJQVALWQMJGE-UHFFFAOYSA-M 0.000 claims description 2
- CRJZNQFRBUFHTE-UHFFFAOYSA-N hydroxylammonium nitrate Chemical compound O[NH3+].[O-][N+]([O-])=O CRJZNQFRBUFHTE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- BJAARRARQJZURR-UHFFFAOYSA-N trimethylazanium;hydroxide Chemical compound O.CN(C)C BJAARRARQJZURR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical class CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 claims 1
- UWKDZWSATBBGBN-UHFFFAOYSA-N 2-[ethyl(methyl)amino]ethanol Chemical compound CCN(C)CCO UWKDZWSATBBGBN-UHFFFAOYSA-N 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 1
- RBLWMQWAHONKNC-UHFFFAOYSA-N hydroxyazanium Chemical compound O[NH3+] RBLWMQWAHONKNC-UHFFFAOYSA-N 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 238000001465 metallisation Methods 0.000 claims 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims 1
- 238000001020 plasma etching Methods 0.000 claims 1
- 125000001425 triazolyl group Chemical group 0.000 claims 1
- 150000007514 bases Chemical class 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 65
- 239000010410 layer Substances 0.000 description 22
- 235000019441 ethanol Nutrition 0.000 description 19
- 239000013047 polymeric layer Substances 0.000 description 19
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 238000003475 lamination Methods 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000908 ammonium hydroxide Substances 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- KEVMYFLMMDUPJE-UHFFFAOYSA-N 2,7-dimethyloctane Chemical group CC(C)CCCCC(C)C KEVMYFLMMDUPJE-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 229940052303 ethers for general anesthesia Drugs 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 241000931526 Acer campestre Species 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 3
- 229960001484 edetic acid Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 3
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229960000834 vinyl ether Drugs 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FOXXZZGDIAQPQI-XKNYDFJKSA-N Asp-Pro-Ser-Ser Chemical compound OC(=O)C[C@H](N)C(=O)N1CCC[C@H]1C(=O)N[C@@H](CO)C(=O)N[C@@H](CO)C(O)=O FOXXZZGDIAQPQI-XKNYDFJKSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/122—Sulfur-containing, e.g. sulfates, sulfites or gypsum
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
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Abstract
本发明涉及一种组合物(例如清洁和/或剥离组合物),其含有(a)0.5‑25重量百分比的碱性化合物;(b)1‑25重量百分比的醇胺化合物;(c)0.1‑20重量百分比的羟铵化合物;(d)5‑95重量百分比的有机溶剂;(e)0.1‑5重量百分比的腐蚀抑制剂化合物;及(f)2‑25重量百分比的水。
Description
相关申请的交叉引用
本申请主张于2015年8月3日申请的美国临时申请序号62/200,236的优先权,该临时申请以全文引用的方式并入本文中。
背景技术
在聚合物膜的激光烧蚀期间,总是形成碎片,且碎片的量及类型取决于膜的组成及烧蚀的加工条件。此碎片大部分沉积在平台上,但一些可到达结构的底部及壁。彻底去除对能够进行进一步的组件构建步骤,诸如焊接及金属沉积而言为必不可少的。在不影响膜的情况下对此类碎片进行化学清洁为本发明的焦点之一。此外,本发明的组合物的设计允许该组合物在高温下充当有效剥离剂。
发明内容
本发明描述一种清洁组合物,其用于室温(例如25℃)下激光烧蚀后清洁制程,也可用作高温(例如65-85℃)下再加工制程和/或后续加工之后的针对聚合物层的剥离组合物。
在一些实施方式中,组合物包含以下(a)-(f)(或基本上由(a)-(f)组成或由(a)-(f)组成):(a)0.5-25重量百分比的碱性化合物;(b)1-25重量百分比的醇胺化合物;(c)0.1-20重量百分比的羟铵化合物;(d)5-95重量百分比的有机溶剂;(e)0.1-5重量百分比的腐蚀抑制剂化合物;及(f)2-25重量百分比的水。
在一些实施方式中,本发明的特征在于一种组合物,其包含以下(a)-(f)(或基本上由以下(a)-(f)组成或由以下(a)-(f)组成):(a)碱性化合物;(b)醇胺化合物;(c)羟铵化合物;(d)有机溶剂;(e)腐蚀抑制剂化合物;及(f)水,其中该组合物的pH值为至少约12,且该有机溶剂具有相对于水约0.5至约0.8的相对能差(RED)。在此类实施方式中,该组合物可具有25℃下约5cSt至约12cSt的动态粘度。
本发明还描述一种激光烧蚀后清洁的方法及一种剥离聚酰亚胺或聚酰亚胺前体组合物的方法。
本发明的组合物的设计中的一独特方面为在室温下,此组合物用作清洁剂来去除激光烧蚀后碎片,且在高温下用作极有效的剥离剂。
具体实施方式
本发明的一些实施方式涉及在激光烧蚀制程后,在不同处理条件下适于清洁残渣的组合物,其还适于剥离聚合物层。当在激光烧蚀后制程之后用作清洁组合物时,基本上半导体基板上很少(若有的话)聚合物层被去除。当用于剥离制程时,关键为去除所有聚合物层且清洁下层基板。本发明人意外地发现本文所述的组合物可有效用于上述清洁与剥离制程。
在一些实施方式中,本文所述的清洁/剥离组合物包括:(a)0.5-25重量百分比的碱性化合物;(b)1-25重量百分比的醇胺化合物;(c)0.1-20重量百分比的羟铵化合物;(d)5-95重量百分比的有机溶剂;(e)0.1-5重量百分比的腐蚀抑制剂化合物;及(f)2-25重量百分比的水。
可用于本发明的清洁/剥离组合物的碱性化合物(a)不受具体限制。在一些实施方式中,碱性化合物包括无机碱,诸如氢氧化钾、氢氧化钠、碳酸钠、碳酸氢钠、碳酸钾及碳酸氢钾;及有机碱,诸如氢氧化季铵。优选的碱性化合物为氢氧化季铵。氢氧化季铵的实例包括,但不限于,氢氧化季铵,所述氢氧化季铵可选自由以下组成的组:四甲基氢氧化铵(TMAH)、2-羟基三甲基氢氧化铵、四乙基氢氧化铵(TEAH)、四丙基氢氧化铵(TPAH)、四丁基氢氧化胺(TBAH)及其混合物。优选的氢氧化季铵为四甲基氢氧化铵及2-羟基三甲基氢氧化铵。更优选的氢氧化季铵为四甲基氢氧化铵。
用于本发明的清洁/剥离组合物的碱性化合物(a)以相对于本发明组合物的总量至少约0.5重量%(例如至少约1重量%、至少约2.5重量%或至少约5重量%)至至多约25重量%(例如至多约20重量%、至多约17.5重量%、至多约15重量%、至多约12.5重量%或至多约10重量%)的量存在。
用于本发明的清洁/剥离组合物的醇胺化合物(b)不受具体限制。这些醇胺化合物包括,但不限于,单乙醇胺(MEA)、二乙醇胺、三乙醇胺、2-(2-氨基乙氧基)乙醇、3-氨基-1-丙醇、氨基-2-丙醇、2-氨基-1-丁醇、5-氨基-1-戊醇、2-氨基-2-甲基-1-丙醇、3-甲基氨基-1-丙醇、4-氨基-1-丁醇、三(羟甲基)氨基乙烷、1-二甲基氨基-2-丙醇、1-氨基-1-环戊烷甲醇、单异丙醇胺、二异丙醇胺、三异丙醇胺、2-异丙氨基乙醇、2-丙基氨基乙醇、2-(叔丁基氨基)乙醇、5-氨基-2,2-二甲基戊醇、2-氨基-3-甲基-1-丁醇、N-甲基氨基乙醇、N-甲基二乙醇胺、N-乙基乙醇胺、N-丁基乙醇胺、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、N,N-二丁基乙醇胺、N-甲基-N-乙基乙醇胺及这些醇胺中的两种或多种的混合物。
用于本发明的清洁/剥离组合物的醇胺化合物(b)以相对于组合物的总量的至少约1重量%(例如至少约2重量%、至少约3重量%或至少约4重量%)至至多约25重量%(例如至多约22.5重量%、至多约20重量%、至多约17.5重量%、至多约15重量%、至多约12.5重量%、至多约10重量%、至多约7.5重量%或至多约5重量%)的量存在。
可用于本发明的清洁/剥离组合物的羟铵化合物(c)不受具体限制。羟铵化合物的实例包括,但不限于,硫酸羟铵、盐酸羟铵、硝酸羟铵、磷酸羟铵、高氯酸羟铵、柠檬酸羟铵及乙酸羟铵。
用于本发明的清洁/剥离组合物的羟铵化合物以相对于组合物的总量至少约0.1重量%(例如至少约0.5重量%、至少约1重量%、至少约1.5重量%或至少约2重量%)至至多约20重量%(例如至多约17重量%、至多约14重量%、至多约11重量%、至多约8重量%或至多约5重量%)的量存在。
本发明组合物中的有机溶剂(d)(例如水溶性有机溶剂)可包括与水高度兼容的有机溶剂,其为例如N-甲基吡咯烷酮(NMP)、N-乙基吡咯烷酮(NEP)、γ-丁内酯、甲基乙基酮(MEK)、二甲亚砜(DMSO)、二甲砜、二甲基甲酰胺、N-甲基甲酰胺、甲酰胺、四甲基脲、四氢糠醇(THFA)及其混合物。在一些实施方式中,有机溶剂选自具有相对于水至多约0.8(例如至多约0.75、至多约0.7)和/或至少约0.5(例如至少约0.55、至少约0.6或至少约0.65)的相对能差(RED)。RED为汉森空间中的汉森参数与汉森空间中的相互作用半径(Ro)之间的距离比(Ra)。Ra由下式定义:(Ra)2=4(δd2-δd1)2+(δp2-δp1)2+(δh2-δh1)2,其中δd、δp及δh分别为分散系之间的能量、分子间作用力及分子之间的氢键。关于汉森参数的更多细节可见于以下参考文献:「Hansen,Charles(2007).Hansen Solubility Parameters:A user's handbook,第二版.Boca Raton,Fla:CRC Press.ISBN 978-0-8493-7248-3」。
在某些实施方式中,有机溶剂(例如水溶性有机溶剂)可为二醇醚。二醇醚可包括二醇单(C1-C6)烷基醚及二醇二(C1-C6)烷基醚,包括,但不限于,(C1-C20)烷二醇、(C1-C6)烷基醚及(C1-C20)烷二醇二(C1-C6)烷基醚。二醇醚的实例包括乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、乙二醇二甲醚、乙二醇二乙醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丙醚、二乙二醇单异丙醚、二乙二醇单丁醚、二乙二醇单异丁醚、二乙二醇单苯甲醚、二乙二醇二甲醚、二乙二醇二乙醚、三乙二醇单甲醚、三乙二醇二甲醚、聚乙二醇单甲醚、二乙二醇甲基乙基醚、三乙二醇乙二醇单甲醚乙酸酯、乙二醇单乙醚乙酸酯、丙二醇单甲醚、丙二醇二甲醚、丙二醇单丁醚、丙二醇、单丙醚、二丙二醇单甲醚、二丙二醇单丙醚、二丙二醇单异丙醚、二亚丙基单丁醚、二丙二醇二异丙醚、三丙二醇单甲醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基丁醇、1,1-二甲氧基乙烷及2-(2-丁氧基乙氧基)乙醇。二醇醚的更典型实例为丙二醇单甲醚、丙二醇单丙醚、三(丙二醇)单甲醚及2-(2-丁氧基乙氧基)乙醇。
本发明的组合物中的优选溶剂为二甲亚砜(DMSO)及四氢糠醇(THFA)。更优选的溶剂为四氢糠醇(THFA)。
用于本发明的清洁/剥离组合物的溶剂以相对于本发明组合物的总量至少约5重量%(例如至少约10重量%、至少约15重量%、至少约20重量%、至少约25重量%、至少约30重量%、至少约35重量%、至少约40重量%或至少约45重量%)至至多约95重量%(例如至多约90重量%、至多约85重量%、至多约80重量%、至多约75重量%、至多约70重量%、至多约65重量%、至多约60重量%、至多约55重量%或至多约50重量%)的量存在。
用于本发明的清洁/剥离组合物的腐蚀抑制剂化合物(e)包括,但不限于,芳族羟基化合物、炔醇、含有羧基的有机化合物及其酸酐以及三唑化合物。
芳族羟基化合物的实例包括,但不限于,苯酚、甲酚、二甲苯酚、邻苯二酚、间苯二酚、氢醌、连苯三酚、1,2,4-苯三酚、水杨醇、对羟基苯甲醇、邻羟基苯甲醇、对羟基苯乙醇、对氨基苯酚、间氨基苯酚、二氨基苯酚、氨基间苯二酚、对羟基苯甲酸、邻羟基苯甲酸、2,4-二羟基苯甲酸、2,5-二羟基苯甲酸、3,4-二羟基苯甲酸及3,5-二羟基苯甲酸。
炔醇的实例包括,但不限于,2-丁炔-1,4-二醇、3,5-二甲基-1-己炔-3-醇、2-甲基-3-丁炔-2-醇、3-甲基-1-戊炔-3-醇、3,6-二甲基-4-辛炔-3,6-二醇、2,4,7,9-四甲基-5-癸炔-4,7-二醇及2,5-二甲基-3-己炔2,5-二醇。
含有羧基的有机化合物及其酸酐的实例包括,但不限于,甲酸、乙酸、丙酸、丁酸、异丁酸、乙二酸、丙二酸、丁二酸、戊二酸、顺丁烯二酸、反丁烯二酸、苯甲酸、邻苯二甲酸、1,2,3-苯三甲酸、乙醇酸、乳酸、苹果酸、柠檬酸、乙酸酐及水杨酸。
三唑化合物可包括三唑、苯并三唑、经取代的三唑及经取代的苯并三唑。三唑化合物的实例包括,但不限于,1,2,4-三唑、1,2,3-三唑或经诸如C1-C8烷基(例如5-甲基三唑)、氨基、硫醇、巯基、亚氨基、羧基及硝基的取代基取代的三唑。特定实例包括苯并三唑、甲苯基三唑、5-甲基-1,2,4-三唑、5-苯基-苯并三唑、5-硝基-苯并三唑、3-氨基-5-巯基-1,2,4-三唑、1-氨基-1,2,4-三唑、羟基苯并三唑、2-(5-氨基-戊基)-苯并三唑、1-氨基-1,2,3-三唑、1-氨基-5-甲基-1,2,3-三唑、3-氨基-1,2,4-三唑、3-巯基-1,2,4-三唑、3-异丙基-1,2,4-三唑、5-苯基硫醇-苯并三唑、卤基-苯并三唑(卤基=F、Cl、Br或I)、萘并三唑及其类似物。
在一些实施方式中,腐蚀抑制剂为结构(I)的肟化合物:
其中R1选自由以下组成的组:氢、经取代或未经取代的C1-C12直链或支链烷基、经取代或未经取代的C5-C10环烷基或杂环烷基及经取代或未经取代的C6-C12芳基或杂芳基;且R2至R5各自独立地选自由以下组成的组:氢、卤素、经取代或未经取代的C1-C12直链或支链烷基、经取代或未经取代的C5-C10环烷基或杂环烷基及经取代或未经取代的C6-C12芳基或杂芳基;或任两个相邻R2至R5(例如R2及R3、R3及R4或R4及R5)连同与其连接的环碳原子一起形成六元环。
在一些实施方式中,R1为氢、经取代或未经取代的C1-C12直链或支链烷基或经取代或未经取代的C6-C12芳基。R1基团的实例包括,但不限于,氢、甲基及苯基。在一些实施方式中,R2至R5各自独立地为氢、卤素、经取代或未经取代的C1-C12直链或支链烷基、经取代或未经取代C5-C10环烷基或杂环烷基或经取代或未经取代的C6-C12芳基或杂芳基。R2-R5基团的实例包括,但不限于,氢、卤素、壬基、十二烷基、苯基、异丙基、叔丁基、环戊基、1,3-二甲基环己基及甲苯基。结构(I)的化合物上的取代基经选择以优化多种参数,包括,但不限于,既定组合物中肟化合物的溶解性及活性以及该组合物的储存稳定性。
适合的结构(I)的化合物的实例包括,但不限于,
用于本发明的清洁/剥离组合物的腐蚀抑制剂化合物以相对于组合物的总量至少约0.1重量%(例如至少约0.2重量%、至少约0.4重量%、至少约0.6重量%、至少约0.8重量%或至少约1重量%)至至多约5重量%(例如至多约4重量%、至多约3重量%、至多约2重量%、至多约1.5重量%、至多约1重量%、至多约0.5重量%或至多约0.3重量%)的量存在。在一些实施方式中,腐蚀抑制剂的优选量为相对于组合物的总量0.2重量%至0.4重量%。
用于本发明的清洁/剥离组合物的水(诸如去离子水、纯水、超纯水等)的量为相对于组合物的总量至少约2重量%(例如至少约4重量%、至少约6重量%或至少约8重量%)至至多约25重量%(例如至多约20重量%、至多约17.5重量%、至多约15重量%、至多约12.5重量%或至多约10重量%)。
本发明的清洁/剥离组合物也可包括一种或多种以下添加剂,其条件为这些添加剂不会不利地影响组合物的剥离和/或清洁效能,也不会破坏下层基板表面:总量多达该组合物的总重量计5重量百分比的表面活性剂、螯合剂、偶联剂、化学改性剂、染料、抗微生物剂和/或其他添加剂。
本发明的清洁/剥离组合物中适合的表面活性剂包括不限于:氟烷基表面活性剂;聚乙二醇;聚丙二醇;聚乙二醇醚;聚丙二醇醚;羧酸盐;十二烷基苯磺酸及其盐;聚丙烯酸酯聚合物;二壬基苯基聚氧乙烯;硅氧烷聚合物;改性的硅氧烷聚合物;炔二醇;改性的炔二醇、烷基铵盐;改性的烷基铵盐;烷基铵磺酸内盐及上述两者或超过两者的组合。适合的表面活性剂的实例包括,但不限于,专利文献JP-A-62-36663、JP-A-61-226746、JP-A-61-226745、JP-A-62-170950、JP-A-63-34540、JP-A-7-230165、JP-A-8-62834、JP-A-9-54432及JP-A-9-5988(以引用的方式并入本文中)中描述的界面活性剂。
螯合剂的实例包括,但不限于,乙二胺四乙酸(EDTA)、羟乙基乙二胺三乙酸(HEDTA)、青霉胺、2,3-二巯基-1-丙磺酸(DMPS)、二巯基丁二酸(DMSA)、葡糖酸、丙烯酸、次氮基三乙酸(NTA)、谷氨酸二乙酸(GLDA;DISSOLVINE(R)GL,来自AkzoNobel,Chicago,Ill.)、亚氨基二丁二酸四钠、亚氨基丁二酸、二乙烯三胺五乙酸五钠及聚天冬胺酸酯。举例而言,螯合剂可为EDTA。
本发明的清洁/剥离组合物可进一步包括偶联剂。偶联剂可帮助稳定化该组合物,诸如维持保存期。偶联剂的实例包括,但不限于,二甲苯磺酸钠(SXS)、异丙苯磺酸钠(SCS)及乙基己基磺酸酯(EHS)。在某些实施方式中,偶联剂为二甲苯磺酸钠。
在一些实施方式中,可自本发明的清洁/剥离组合物排除一种或多种以下物质。实例包括活性含氟化合物,其进行水解以释放氟(例如潜在HF源,诸如羧基氟化物);氟化物盐,诸如氟化铵或氟化季铵;氧化剂,诸如过氧化物及无机氧化剂;脒盐,诸如胍盐、乙酰胺鎓盐及甲酰胺鎓盐;脲及脲衍生物;以及酚类化合物。
本发明的清洁/剥离组合物可具有碱性pH值。pH值可为至少约12(例如至少约12.2、至少约12.4、至少约12.6、至少约12.8、至少约13、至少约13.2、至少约13.4、至少约13.6、至少约13.8或至少约14)和/或至多约16.0(例如至多约15.8、至多约15.6、至多约15.4、至多约15.2、至多约15.0、至多约14.8、至多约14.6、至多约14.4或至多约14)。优选的pH值范围为13.5至15.5。最优选的pH值范围为14至15.3。该组合物的pH值可通过可使用标准水性缓冲溶液校准的pH计测量。不希望受理论束缚,据信相对较高的pH值(亦即强碱性条件)可促进该组合物在清洁制程中去除激光烧蚀后碎片或在剥离制程中去除聚合物层。举例而言,在去除激光烧蚀后碎片的清洁制程中,碱性条件可中和酸性物质且使其可溶于水溶液。在去除聚合物层的剥离制程中,碱性条件可促进聚合体链或交联网络断裂,因此帮助去除聚合物层。
在一些实施方式中,本发明的清洁/剥离组合物可具有相对较低的动态粘度。在一些实施方式中,本发明中清洁/剥离组合物的动态粘度可为至少约5.0cSt(例如至少约5.3cSt、至少约5.6cSt、至少约6.0cSt、至少约6.3cSt、至少约6.6cSt、至少约7.0cSt、至少约7.3cSt、至少约7.6cSt、至少约8.0cSt、至少约8.3cSt或至少约8.6cSt)和/或至多约12cSt(例如至多约11.6cSt、至多约11.3cSt、至多约11.0cSt、至多约10.6cSt、至多约10.3cSt、至多约10cSt、至多约9.6cSt、至多约9.3cSt或至多约9.0cSt)。如本文所用,动态粘度在25℃下通过使用经校准的Cannon-Fenske常规粘度计测量。不希望受理论束缚,据信具有相对较高动态粘度的组合物可具有较低的清洁/剥离能力,至少因为该组合物中的活性成分扩散至聚合物层中可具有相对较低的速率(与具有相对较低动态粘度的组合物比较),此可导致较低的剥离和/或清洁能力。
本发明的清洁/剥离组合物可通过使用常规混合法以任何适合次序混合各种组分来制备。这些组分可被冷混合,不需要加热。
在一些实施方式中,本发明的清洁/剥离组合物可用于半导体基板上聚合物膜的激光烧蚀之后的清洁制程中。在一些实施方式中,此组合物还可用于剥离半导体基板上未曝光的感光性聚合物膜、曝光的交联聚合物膜或非感光性聚合物膜的制程中。
半导体基板可为圆形(诸如晶圆)或可为长条。在一些实施方式中,半导体基板可为硅基板、铜基板、铝基板、氧化硅基板、氮化硅基板、玻璃基板、有机层压基板或介电材料基板。
除了由在用于激光烧蚀的微粒波长下聚合物膜的吸光度限制之外,用于形成半导体基板上的聚合物膜的聚合物组合物不受具体限制。聚合物层可为聚酰亚胺层、聚酰亚胺前体层、聚(甲基)丙烯酸酯层、聚氨基甲酸酯层、聚苯并恶唑层、聚苯并噻唑层、酚醛清漆层、环氧树脂层、聚酰胺层或聚酯层。聚合物层可为感光性或非感光性,且可通过旋涂、喷涂、辊涂、浸涂含有聚合物组合物的溶液或使用层压机层压感光性或非感光性干膜组合物来形成。优选的聚合物层为感光性聚酰亚胺层及感光性聚酰亚胺前体层。可用于形成此类层的感光性聚酰亚胺组合物或感光性前体组合物不受具体限制且包括,但不限于以引用的方式并入本文中的专利文献US5449588、US4661435、US8932801、US2009202793、US6160081、US7648815、US6875554及US2014178823中揭示的组合物。
在一些实施方式中,优选的聚合物组合物包括:(a)至少一种任选地具有封端基团的可溶性聚酰亚胺聚合物,所述封端基团含有至少一种选自经取代或未经取代的直链烯基(例如C2-C6直链烯基)及经取代或未经取代的直链烯基(例如C2-C6直链炔基)的官能团;(b)至少一种反应性官能化合物(RFC);(c)至少一种引发剂;及(d)至少一种溶剂。
可溶性聚酰亚胺聚合物定义为在有机溶剂中诸如γ-丁内酯(GBL)、己内酯、环丁砜、N-甲基-2-吡咯烷酮(NMP)、N-乙基-2-吡咯烷酮、N-丁基-2-吡咯烷酮、N-甲酰基吗啉、二甲基咪唑啶酮、N-甲基己内酰胺、N-甲基丙烯酰胺、N,N-二甲基乙酰胺(DMAc)、二甲亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)、N,N-二乙基甲酰胺、二乙基乙酰胺、四氢糠醇(THFA)、碳酸丙烯酯、2-苯氧基乙醇、丙二醇苯基醚、苯甲醇、甲基乙基酮(MEK)、甲基异丁基酮(MIBK)、2-庚酮、环戊酮(CP)、环己酮、丙二醇单甲醚乙酸酯(PGMEA)、乳酸乙酯(EL)、乙酸正丁酯(n-BA)或其混合物中的溶解度为5wt%或更高的聚合物。
本文所述的聚合物组合物中反应性官能化合物(RFC)一般具有至少一个能够与聚酰亚胺聚合物上任选的封端官能团(例如上述聚酰亚胺聚合物上封端官能团)反应的官能团或与聚酰亚胺聚合物上另一反应性官能团反应的官能团。RFC可为单体或寡聚物。寡聚物可含有许多单体单元且能够进一步反应以掺入最终物质中。此类单体单元/寡聚物的实例基于一种或多种以下类型:丙烯酸酯、酯、乙烯醇、氨基甲酸酯、脲、酰亚胺、酰胺、咔唑、碳酸酯、吡喃糖、硅氧烷、尿素-甲醛及三聚氰胺-甲醛。RFC一般含有至少一个末端和/或侧接反应性官能团,其能够与聚酰亚胺聚合物上至少一个选自经取代或未经取代的直链烯基及经取代或未经取代的直链炔基的官能团进行自由基、热或酸催化反应。在一个实施方式中,RFC上反应性官能团包括不饱和双键或三键。
RFC上反应性官能团的适合的实例包括,但不限于,乙烯基、烯丙基、乙烯醚基、丙烯醚基、(甲基)丙烯酰基、环氧基、-SiH基及-SH(硫醇)基。
在一个实施方式中,RFC的适合的实例包括,但不限于,氨基甲酸酯丙烯酸酯寡聚物。术语「氨基甲酸酯丙烯酸酯寡聚物」是指含有氨基甲酸酯键且具有(甲基)丙烯酸酯(例如丙烯酸酯或甲基丙烯酸酯)官能团的一类化合物,诸如氨基甲酸酯多(甲基)丙烯酸酯、多氨基甲酸酯(甲基)丙烯酸酯及多氨基甲酸酯多(甲基)丙烯酸酯。氨基甲酸酯(甲基)丙烯酸酯寡聚物类型已通过例如Coady等人的美国专利第4,608,409号及Chisholm等人的美国专利第6,844,950号(以引用的方式并入本文中)描述。RFC的其他特定实例包括1,6-己二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、二乙烯基苯、乙氧基化双酚A-二(甲基)丙烯酸酯、二乙二醇双(烯丙基碳酸酯)、三羟甲基丙烷三(甲基)丙烯酸酯、二-三羟甲基丙烷四(甲基)丙烯酸酯、异戊四醇三(甲基)丙烯酸酯、异戊四醇四(甲基)丙烯酸酯、二异戊四醇五/六(甲基)丙烯酸酯、异氰尿酸酯三(甲基)丙烯酸酯、双(2-羟乙基)-异氰尿酸酯二(甲基)丙烯酸酯、1,3-丁二醇三(甲基)丙烯酸酯、1,4-丁二醇三(甲基)丙烯酸酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸苯甲酯、新戊二醇二(甲基)丙烯酸酯、(甲基)丙烯酸酯改性的尿素-甲醛树脂、(甲基)丙烯酸酯改性的三聚氰胺-甲醛树脂及(甲基)丙烯酸酯改性的纤维素。
在一些实施方式中,RFC化合物为含硅的二(甲基)丙烯酸酯化合物。
含有硫醇基的RFC化合物的实例包括,但不限于,三羟甲基丙烷三(巯基乙酸酯)、异戊四醇四(巯基乙酸酯)、二异戊四醇六(3-巯基丙酸酯)及乙氧基化三羟甲基丙烷三-3-巯基丙酸酯。含有乙烯醚基的RFC化合物的实例包括,但不限于,1,4-丁二醇二乙烯基醚、1,4-环己烷二甲醇二乙烯基醚、二(乙二醇)乙烯醚、聚(乙二醇)二乙烯基醚及双[4-(乙烯基氧基)丁基](4-甲基-1,3-亚苯基)双氨基甲酸酯。含有SiH基团的RFC化合物的一个实例为可购自Hybrid Plastics的八硅烷SH1310。
用于聚合物组合物中的组分(c)中的引发剂(例如光引发剂)为当组合物或一部分组合物曝露于光和/或热时,能够引发聚酰亚胺聚合物上的官能团与反应性官能化合物之间的反应的化合物。用于该组合物中的一些引发剂通过在加热时产生自由基或通过在曝露波长下吸收光来起作用。用于该组合物中的其他引发剂通过在加热时产生酸或通过在曝露波长下吸收光来起作用。用于该组合物中的其他引发剂通过在加热时产生碱性化合物或通过在曝露波长下吸收光来起作用。在一些实施方式中,本文所述的引发剂还可催化聚酰亚胺聚合物上的官能团与反应性官能化合物之间的反应,因此还用作催化剂。
在加热时产生自由基的引发剂的特定实例包括,但不限于,过氧化物(诸如过氧化苯甲酰、过氧化环己酮、过氧化物月桂酰、过氧苯甲酸叔戊酯、叔丁基过氧化氢、过氧化二异丙苯、氢过氧化异丙苯、过氧化丁二酸或二(正丙基)过氧化二碳酸酯)、偶氮化合物(例如2,2-氮杂双(异丁腈)、2,2-氮杂双(2,4-二甲基戊腈)、二甲基-2,2-氮杂双异丁酸酯、4,4-氮杂双(4-氰基戊酸)、氮杂双环己烷甲腈或2,2-氮杂双(2-甲基丁腈))、α-羟基酮(例如1-羟基-环己基-苯基-酮(Irgacure 184))及其混合物。
在该聚合物膜中含有开放的通孔的图案化的聚合物膜可通过用激光束照射该聚合物膜来形成。此制程称为激光钻孔或激光烧蚀。使用激光束的直接激光烧蚀为基于具有高纵横比的细通孔的掩模图案的干式单步材料去除。此项技术通常用于行业中。在一些实施方式中,激光烧蚀可使用一种或多种基于掩模的投影准分子激光实现。在一些实施方式中,此制程可通过无掩模的直接烧蚀固态激光进行。在一些实施方式中,激光波长为355nm或更少。在一些实施方式中,激光波长为308nm或更少。适合激光烧蚀方法的实例包括,但不限于专利文献US7598167、US6667551及US6114240(以引用的方式并入本文中)中描述的方法。
该激光烧蚀制程的副产物为残渣或灰尘(碎片),其作为激光烧蚀制程的结果产生。碎片累积在通孔的侧壁及底部中。其还累积在激光成像装置的镜子及光学装置上。这可对激光烧蚀制程的效能具有不利影响。装配至成像器中的真空装置可在光学装置及镜子上捕捉大量残渣。若干技术用于激光烧蚀后通孔的清洁。这些技术包括使用牺牲层、溶剂清洁、氧等离子体清洁、CO2雪清洁及使用皮秒DPSS激光的DPSS清洁(二极管泵固态)。适合的激光烧蚀后清洁法的实例包括,但不限于,专利文献US7994450、US20120168412、US20020170894、US20030052101及US8716128(以引用的方式并入本文中)中描述的方法。
在一个实施方式中,制造半导体装置的方法包含以下步骤:(i)在烧蚀条件下将聚合物膜曝露于激光;及(ii)使用一种或多种本发明的组合物清洁激光烧蚀碎片。
除受在用于激光烧蚀的微粒波长下的聚合物膜的吸光度限制之外,聚合物组合物不受具体限制。材料吸收激光能量的能力限制该能量可进行适用的烧蚀的深度。烧蚀深度通过例如材料的吸收深度及加工材料的汽化热来确定。深度还为射束能密度、激光脉冲持续时间及激光波长的函数。加工材料上每单位面积的激光能量根据能量流量测量。在一个实施方式中,聚合物组合物可被调整至具有在248nm每微米0.007至每微米0.015的吸光度。在另一个实施方式中,聚合物组合物可被调整至具有在308nm每微米0.6至每微米0.9的吸光度。在又一个实施方式中,聚合物组合物可被调整至具有在355nm每微米0.1至每微米0.2的吸光度。在一些实施方式中,吸收的量可通过添加染料调整。在所有此三个实施方式中,能量流量为至多2000mJ/cm2(例如至多1900mJ/cm2、至多1800mJ/cm2、至多1700mJ/cm2或至多1600mJ/cm2)和/或至少1200mJ/cm2(例如1300mJ/cm2、至少1400mJ/cm2或至少1500mJ/cm2)。通过此类聚合物组合物形成的聚合物层的膜厚度可为至少约1微米(例如至少约2微米、至少约5微米、至少约10微米、至少约15微米、至少约20微米、至少约25微米、至少约30微米、至少约35微米、至少约40微米或至少约45微米)至至多约80微米(例如至多约75微米、至多约70微米、至多约65微米、至多约60微米、至多约55微米或至多约50微米)。
激光烧蚀后清洁制程可通过使用已知技术,诸如浸入、离心喷雾、超高速清洁及超音波清洁,用本发明的组合物处理待清洁的目标来实现。此类清洁程序的实例揭示于以引用的方式并入本文中的专利文献US6766813、US5100476及US5368054中。
用于清洁制程中的温度可为至少约15℃(例如至少约16℃、至少约17℃、至少约18℃、至少约19℃、至少约20℃、至少约21℃、至少约22℃或至少约23℃)和/或至多约30℃(例如至多约29℃、至多约28℃、至多约27℃、至多约26℃或至多约25℃)。用于清洁制程中的时间可为至少约2分钟(例如至少约4分钟或至少约5分钟)及至多约10分钟(例如至多约8分钟或至多约6分钟)。
清洁制程中的任选步骤包括清洗及干燥步骤。半导体基板可用水或水溶液清洗。可用于此制程中的水溶液可为DI水与表面活性剂的混合物、含有表面活性剂的微碱性水溶液或含有直链或支链C1-C4醇的水溶液以去除本发明中描述的组合物和/或其他残渣。此步骤也可通过使用已知技术,诸如浸入、离心喷雾、超高速清洁及超音波清洁来实现。经清洁的半导体基板可使用本领域技术人员已知的干燥方式干燥。
意外地,本发明中描述的组合物显示出预料不到的效果:在低温下从该图案化的聚合物膜完全去除激光烧蚀后碎片且对该膜无任何破坏。
在一些实施方式中,在高温下,本发明的组合物也可用于从半导体基板剥离未曝光的感光性聚合物膜、曝光的交联聚合物膜或非感光性聚合物膜的制程中。剥离制程可通过使用已知技术,诸如浸入、离心喷雾、超高速清洁及超音波清洁处理待剥离聚合物膜的目标来实现。
用于剥离制程中的温度可为至少约65℃(例如至少约67℃或至少约70℃)至至多约85℃(例如至多约80℃或至多约75℃)。剥离时间可为至少约15分钟(例如至少约30分钟、至少约40分钟、至少约50分钟或至少约60分钟)和/或至多约120分钟(例如至多约110分钟、至多约100分钟、至多约90分钟、至多约80分钟或至多约70分钟)。
剥离制程中的任选步骤包括如上在清洁制程中所述的清洗及干燥步骤。
本发明的组合物的设计中的独特方面为本发明的组合物可用作在室温下激光烧蚀后碎片的清洁剂,且可用作用于在高温下完全剥离聚合物膜的非烧蚀区域的极有效的剥离剂。
当前公开的一个实施方式的特征在于一种用于制造半导体装置的方法。此方法可例如通过以下进行:(i)将基板上的感光性聚合物层(例如含有聚酰亚胺聚合物或聚酰亚胺前体聚合物的层)图案化(例如通过用聚合物组合物涂布基板形成)以形成图案化的聚合物层;(ii)用离子注入(例如为了形成晶体管)、等离子体或湿式蚀刻(例如为了在感光性聚合物层中形成图案)或金属沉积(例如为了形成装置之间的导电连接)处理图案化的基板;及(iii)使用本文所述的组合物剥离该聚合物层。以上三个步骤每一个可通过此项技术中已知的方法进行。在一些实施方式中,聚合物层可通过聚酰亚胺组合物或聚酰亚胺前体组合物形成。在一些实施方式中,聚酰亚胺组合物或聚酰亚胺前体组合物可为感光性的。
本发明的一个实施方式的特征在于一种方法,其包括以下步骤:(i)提供含有聚合物膜的半导体基板;(ii)任选地通过使用光或其他辐射源整片曝露该聚合物膜;(iii)任选地使曝光处理后的该聚合物膜经受曝露后烘烤处理;(iv)任选地使经曝露后烘烤的膜经受硬性烘烤;(v)通过激光烧蚀制程,使用激光在该聚合物膜中开通孔以形成图案化的聚合物膜;(vi)使用本发明的清洁/剥离组合物从该图案化的聚合物膜去除激光烧蚀后碎片;(vii)通过将熔融导电膏施加至通孔上在包括通孔内侧的区域中形成导电柱;(viii)任选地用导电膏去除剂溶液清洗图案化的聚合物膜,以从聚合物膜顶部去除导电膏;(ix)在高温下使用本发明的清洁/剥离组合物去除聚合物膜的非烧蚀区域;以及(x)任选地用水或水溶液清洗图案化的聚合物膜以去除本发明的任何残留的清洁/剥离组合物及其他残渣。用于清洁步骤(vi)的清洁/剥离组合物可与剥离步骤(ix)中所用的清洁/剥离组合物相同或不同。
在此制程的一些实施方式中,聚合物膜为感光性的。在一些实施方式中,感光性膜为负型色调。在一些实施方式中,感光性负型色调膜由聚酰亚胺组合物或聚酰亚胺前体组合物形成。
在此制程的一些实施方式中,在步骤(ii)中感光性聚合物涂布的基板被曝露于放射线。曝露通常为整片曝露,在非烧蚀条件下进行。一般而言,此曝露步骤引起曝露区域中感光性聚合物涂层固化或交联。此曝露步骤使用光或其他辐射源(例如紫外光、可见光、电子束放射线或X射线),如适于特定聚合物组合物中的引发剂。使用i-线(365nm)、h-线(405nm)或g-线(436nm)紫外光为优选的。本领域技术人员将已知何种类型高能辐射适于既定应用。用于本发明中的能量剂量可为至少约200mJ/cm2(例如至少约300mJ/cm2、至少约400mJ/cm2、至少约500mJ/cm2、至少约600mJ/cm2、至少约700mJ/cm2或至少约800mJ/cm2)至至多约2000mJ/cm2(例如至多约1800mJ/cm2、至多约1600mJ/cm2、至多约1400mJ/cm2、至多约1200mJ/cm2或至多约1000mJ/cm2)。
在一些实施方式中,进行短暂曝露后烘烤。曝露后烘烤温度可为至少约50℃(例如至少约60℃、至少约70℃或至少约80℃)和/或至多约120℃(例如至多约110℃、至多约100℃、至多约100℃及至多约90℃)。曝露后烘烤时间可为至少约120秒(例如至少约150秒或至少约180秒)和/或至多约300秒(例如至多约270秒或至多约240秒)。
在一些实施方式中,可包含硬性烘烤(hard baking)步骤。在一些实施方式中,硬性烘烤温度可为至少约150℃(例如至少约170℃或至少约190℃)至至多约250℃(例如至多约230℃或至多约210℃)。硬性烘烤时间可为至少约30分钟(例如至少约45分钟或至少约60分钟)和/或至多约120分钟(例如至多约105分钟或至多约90分钟)。
激光烧蚀步骤及激光烧蚀后清洁步骤可如先前所述进行。
在此制程的下一步中,可通过在由激光烧蚀制程产生的通孔中形成导电层来提供半导体基板的一个表面与另一基板的一个表面之间的电连接。在不必用熔融材料(例如熔融导电膏或焊膏)填充通孔的情况下形成该导电层为一种确保高度可靠电连接的可能方式。导电膏或焊膏包括金属或合金,诸如镍、铜、铍铜、镍合金、铜合金、铍铜合金、镍钴铁合金及铁镍合金与聚合物粘合剂。该组合物及导电膏应用的更多细节描述于以引用的方式并入本文中的专利文献US2013069014、US4789411、US5204025及US7081214中。用于在回流后去除导电膏的清洁组合物描述于以引用的方式并入本文中的专利文献US5888308及US6277799中。清洁制程可通过使用已知技术,诸如先前所述的浸入、离心喷雾、超高速清洁及超音波清洁来实现。
可通过在包括任选的清洗及干燥步骤的剥离制程中,使用如上所述的本发明的清洁/剥离组合物完全去除(剥离)聚合物膜。
经清洁的半导体基板准备用于随后集成制程以产生半导体装置,诸如半导体封装(例如存储器封装、微处理器封装、平板封装及用于移动装置的封装)。在一些实施方式中,半导体封装可通过多步骤制程制备,该多步骤制程包括至少一个使用本文所述的清洁/剥离组合物去除激光烧蚀或钻孔后碎片的步骤。在一些实施方式中,半导体封装可通过多步骤制程制备,该多步骤制程包括至少一个使用本文所述的清洁/剥制程离组合物剥离或去除聚合物膜的步骤。
本发明现将参考以下非限制性实例进一步阐明。
合成实例1(Poly-1)
聚合反应在一升三颈夹套圆底烧瓶中进行,该烧瓶装备有机械搅拌器、热电偶及氮气入口以保持整个反应中正氮气压力。向烧瓶充入203.7克二苯甲酮-3,3',4,4'-四甲酸二酸酐(BTDA)、70.2克六氟亚异丙基二邻苯二甲酸酐(6FDA)及300克无水NMP。将内含物在18-20℃下搅动。使106.55克1-(4-氨基苯基)-1,3,3-三甲基茚满-5-胺(DAPI)及60.4克2,4-二氨基-1,3,5-三甲苯(DAM)溶于瓶中700克无水NMP中。在室温下将二胺溶液通过泵添加至烧瓶,历时1小时。混合物升温至60℃且搅动3小时,以产生聚酰胺酸。
为将以上形成的聚酰胺酸封端,将16.5克1,3-二氧-1,3-二氢-2-苯并呋喃-5-甲酸3-丙烯酰基氧基-2,2-双[(丙烯酰基氧基)甲基]丙酯(PETA)及1.58g吡啶充入烧瓶中。将混合物在60℃下搅动3小时,以形成封端的聚酰胺酸。
为进行以上封端聚酰胺酸的亚胺化反应,将100.0克乙酸酐及35.0克吡啶充入烧瓶。使反应混合物升温至110℃且搅动12小时。抽出少量样品(1g)且在50:50甲醇:水(10ml)中沉淀。固体通过过滤分离且干燥。FTIR分析展示亚胺化反应完成(展示不存在酰胺及酸酐峰)。
溶液冷却至室温且逐滴添加至18升用力搅拌的去离子水以使聚合物沉淀。聚合物通过过滤收集且用一升去离子水洗涤。饼状物用四升甲醇重新形成浆液且过滤。湿饼状物在空气中干燥12小时,接着聚合物在真空下在70℃下干燥12小时。所得聚酰亚胺聚合物的分子量通过GPC测量。
组合物实例1
配制聚合物溶液用于制备干膜(F-1)
向装备有机械搅拌器的三颈圆底烧瓶添加645份GBL、205.4份合成实例1中获得的聚合物、6.6份(3-缩水甘油基氧基丙基)三甲氧基硅烷、6.16份NCI-831(商品名,可购自ADEKA公司)、4.11份氧化(2,4,6-三甲基苯甲酰基)膦、69.32份二丙烯酸四亚乙酯、23.11g异戊四醇三丙烯酸酯及30.81g结构PAE-1的聚酰胺酸酯。将组合物机械搅拌18小时。接着通过使用0.2μm过滤器(来自Meissner Filtration Product,Inc.的Ultradyne,目录号CFTM10.2-44B1)过滤此组合物。
干膜实例DF-1
经过滤的感光性溶液(F-1)经由来自Frontier Industrial Technologies(Towanda,PA)的夹缝式涂布机以5英尺/分钟(每分钟150cm)的线速度施加至用作载体基板的未经线上电晕处理的厚度为36μm的聚对苯二甲酸亚乙酯(PET)膜TA30(Toray PlasticsAmerica,Inc.制造)上,且在180-200℉干燥以获得厚度为37微米的聚合物层。层压压力为30psi且真空为0.7托。在此聚合物层上,双轴定向聚丙烯(BOPP)膜(通过IMPEX GLOBAL LLC制造,商品名80ga BOPP)通过辊压层压以充当保护层。
干膜实例的层压(L-1)
在通过剥离去除保护层后,干膜结构DF-1的聚合物层(6″×6″)置于4″铜晶圆(Wafernet)上。通过在80℃真空层压,接着经受25psi的压力,将聚合物层层压至Cu涂布的晶圆上。通过使用OPTEK,NJ制造的DPL-24A分压层压机进行层压制程。
干膜实例的层压(L-2)
在通过剥离去除保护层后,干膜结构DF-1的聚合物层(12″×12″)置于8″铜晶圆(Wafernet,条目号S45102)上。通过在80℃下真空层压,接着经受25psi的压力,将聚合物层层压至Cu涂布的晶圆上。通过使用OPTEK,NJ制造的DPL-24A分压层压机进行层压过程。
干膜实例的激光烧蚀(LA-1)
层压干膜(L-2)使用SUSS宽带曝光工具在1000mJ/cm2下整片曝露。接着晶圆在50℃下加热180秒。层压的干膜接着在220℃下在真空下烘烤1小时。
通过EPL300Gen2,在308nm波长下,使用通孔直径为65微米且间距为90微米的通孔掩模,对曝露的烘烤晶圆进行激光烧蚀程序。308nm激光的印刷能量固定在800mJ/cm2及N=60脉冲。
清洁/剥离组合物的实例
组合物通过使用2.5份氢氧化四甲基铵(TMAH)、4.3份单乙醇胺、0.5份硫酸羟铵、85份四氢糠醇(THFA)、0.2份5-甲基-1H-苯并三唑及7.5份水制备。通过使用装备有MetrohmpH电极部件#6.0233/100的Metrohm型号716基本单元,测得此清洁/剥离组合物的pH值为14.9。通过使用Cannon Fenske粘度计型号150,在25℃测量清洁/剥离组合物的动态粘度。动态粘度为8.5cSt。
清洁程序的实例
将层压晶圆LA-1切成1″×2″片,且垂直置于含有300mL以上获得的清洁/剥离组合物的600mL烧杯中。烧杯内含物使用磁棒在25℃下搅拌。通过使用调温器维持温度恒定。5分钟后,去除晶圆片且立刻用水清洗且通过使用氮气吹洗来干燥。在金溅射后,通过使用光学显微镜及通过SEM测定清洁有效性。晶圆的俯视图及横截面影像揭露清洁后无残渣。膜厚度损失程度通过使用Dektak表面亮度仪测量残余膜的厚度来测定。烧蚀碎片被完全去除且对膜没有任何破坏。未观测到膜厚度损失。
剥离程序的实例
将层压晶圆LA-1切成1″×2″片,且垂直置于含有300mL以上获得的清洁/剥离组合物的600mL烧杯中。烧杯内含物使用磁棒在85℃下搅拌。通过使用调温器维持温度恒定。60分钟后,去除晶圆片且立刻用水清洗且通过使用氮气吹洗来干燥。在金溅射后,通过使用光学显微镜及通过SEM测定剥离有效性。晶圆的俯视图及横截面影像揭露清洁后无残渣。膜厚度损失程度通过使用Dektak表面亮度仪测量残余膜的厚度来测定。观测到激光烧蚀后残留的聚合物层的完全剥离。
Claims (25)
1.一种组合物,包含:
(a)0.5-25重量百分比的碱性化合物;
(b)1-25重量百分比的醇胺化合物;
(c)0.1-20重量百分比的羟铵化合物;
(d)5-95重量百分比的有机溶剂;
(e)0.1-5重量百分比的腐蚀抑制剂化合物;及
(f)2-25重量百分比的水。
2.如权利要求1所述的组合物,其中,所述碱性化合物选自由以下所组成的组:四甲基氢氧化铵(TMAH)、2-羟基三甲基氢氧化铵、四乙基氢氧化铵(TEAH)、四丙基氢氧化铵(TPAH)、四丁基氢氧化胺(TBAH)及其混合物。
3.如权利要求1所述的组合物,其中,所述醇胺化合物选自由以下所组成的组:单乙醇胺(MEA)、二乙醇胺、三乙醇胺、2-(2-氨基乙氧基)乙醇、单异丙醇胺、二异丙醇胺、三异丙醇胺、N-甲基二乙醇胺、N-乙基乙醇胺、N-丁基乙醇胺、二乙醇胺、二甘醇胺、2-(2-氨基乙氧基)乙醇、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、N,N-二丁基乙醇胺、N-甲基-N-乙基乙醇胺及其混合物。
4.如权利要求1所述的组合物,其中,所述羟铵化合物选自由以下所组成的组:硫酸羟铵、盐酸羟铵、硝酸羟铵及磷酸羟铵。
5.如权利要求4所述的组合物,其中,所述羟铵化合物为硫酸羟铵。
6.如权利要求1所述的组合物,其中,所述溶剂选自由以下所组成的组:N-甲基吡咯烷酮(NMP)、N-乙基吡咯烷酮(NEP)、γ-丁内酯、甲基乙基酮(MEK)、二甲亚砜(DMSO)、二甲砜、二甲基甲酰胺、N-甲基甲酰胺、甲酰胺、四甲基脲、四氢糠醇(THFA)及其混合物。
7.如权利要求6所述的组合物,其中,所述溶剂为二甲亚砜(DMSO) 或四氢糠醇(THFA)。
8.如权利要求1所述的组合物,其中,所述腐蚀抑制剂为三唑、苯并三唑、经取代的三唑或经取代的苯并三唑。
9.如权利要求8所述的组合物,其中,所述腐蚀抑制剂为5-甲基-1H-苯并三唑。
10.如权利要求9所述的组合物,其中,所述腐蚀抑制剂的量为总组合物的至多约0.5重量%。
11.如权利要求9所述的组合物,其中,所述腐蚀抑制剂的量为总组合物的至多约0.3重量%。
12.如权利要求1所述的组合物,其中,所述腐蚀抑制剂为结构(I)的化合物
其中
R1选自由以下所组成的组:氢、经取代或未经取代的C1-C12直链或支链烷基、经取代或未经取代的C5-C10环烷基或杂环烷基及经取代或未经取代的C6-C12芳基或杂芳基;且
R2至R5各自独立地选自由以下所组成的组:氢、卤素、经取代或未经取代的C1-C12直链或支链烷基、经取代或未经取代的C5-C10环烷基或杂环烷基及经取代或未经取代的C6-C12芳基或杂芳基;或任两个相邻R2至R5连同与其连接的环碳原子一起形成六元环。
13.如权利要求12所述的组合物,其中,所述腐蚀抑制剂为
。
14.一种用于制造半导体装置的方法,包括在约65℃至约85℃的温度下,用如权利要求1至13中任一项所述的组合物处理半导体基板上未曝光的感光性聚合物膜、曝光的交联聚合物膜或非感光性聚合物膜。
15.一种用于制造半导体装置的方法,包括以下步骤:
(i)使半导体基板的顶部上的包含至少一种聚酰亚胺聚合物或聚酰亚胺前体聚合物的感光性聚合物膜图案化以形成图案化的膜;
(ii)用离子注入、等离子体蚀刻或湿式蚀刻或金属沉积处理所述图案化的膜,以及
(iii)使用如权利要求1至13中任一项所述的组合物剥离所述感光性聚合物膜。
16.一种用于制造半导体装置的方法,包括以下步骤:
(i)在烧蚀条件下将聚合物膜曝露于激光;及
(ii)使用如权利要求1至13中任一项所述的组合物清洁激光烧蚀后碎片。
17.一种方法,包括:
(i)提供含有聚合物膜的半导体基板;
(ii)任选地通过使用光或另一其他辐射源整片曝露所述聚合物膜;
(iii)任选地在曝光处理后使所述聚合物膜经受曝露后烘烤处理;
(iv)任选地使经曝露后烘烤的聚合物膜经受硬性烘烤;
(v)通过使用激光的激光烧蚀制程在所述聚合物膜中开通孔,以形成图案化的聚合物膜;
(vi)通过使用组合物,从所述图案化的聚合物膜去除激光烧蚀后碎片;
(vii)通过将熔融导电膏施加至通孔而在包括通孔内侧的区域中形成导电柱;
(viii)任选地用导电膏去除剂溶液清洗所述图案化的聚合物膜以从聚合物膜的顶部去除所述导电膏,
(ix)在高温下使用组合物去除所述图案化的聚合物膜的非烧蚀区域;以及
(x)任选地用水或水溶液清洗所述图案化的聚合物膜以去除残渣,
其中步骤(vi)及(ix)中所使用的组合物为如权利要求1至13中任一项所述的组合物。
18.如权利要求17所述的方法,其中,所述基板为铜且所述聚合物膜由包含(a)至(d)的组合物获得:
(a)至少一种具封端基团的可溶性聚酰亚胺聚合物,所述封端基团具有至少一种选自经取代或未经取代的直链烯基和经取代或未经取代的直链炔基的官能团;
(b)至少一种反应性官能化合物(RFC);
(c)至少一种引发剂;及
(d)至少一种溶剂。
19.如权利要求18所述的方法,其中,激光烧蚀通过使用基于掩模的投影准分子激光实现。
20.如权利要求18所述的方法,其中,所述激光的波长为355nm或更少。
21.如权利要求18所述的方法,其中,所述激光的波长为308nm或更少。
22.一种通过多步骤制程制备的半导体封装,所述多步骤制程包括至少一个步骤,所述至少一个步骤包括使用如权利要求1至13中任一项所述的组合物去除激光烧蚀后碎片。
23.一种通过多步骤制程制备的半导体封装,所述多步骤制程包括至少一个步骤,所述至少一个步骤包括使用如权利要求1至13中任一项所述的组合物剥离聚合物膜。
24.一种组合物,包含:
(a)碱性化合物;
(b)醇胺化合物;
(c)羟铵化合物;
(d)有机溶剂;
(e)腐蚀抑制剂化合物;及
(f)水,
其中,所述组合物的pH值为至少约12,且所述有机溶剂具有相对于水约0.5至约0.8的相对能差(RED)。
25.如权利要求24所述的组合物,其中,所述组合物具有在25℃下约5cSt至约12cSt的动态粘度。
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CN110597026A (zh) * | 2019-09-26 | 2019-12-20 | 上海富柏化工有限公司 | 一种软性电路板干膜清除工艺 |
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CN108026491B (zh) | 2021-08-13 |
JP2018526495A (ja) | 2018-09-13 |
KR102637508B1 (ko) | 2024-02-15 |
JP6808714B2 (ja) | 2021-01-06 |
KR20180029080A (ko) | 2018-03-19 |
TW201715036A (zh) | 2017-05-01 |
EP3331978A1 (en) | 2018-06-13 |
US10696932B2 (en) | 2020-06-30 |
WO2017023677A1 (en) | 2017-02-09 |
TWI790194B (zh) | 2023-01-21 |
EP3331978A4 (en) | 2018-07-11 |
EP3331978B1 (en) | 2024-10-09 |
US20190016999A1 (en) | 2019-01-17 |
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