US20060214139A1 - Methods for producing a dielectric, dielectric having self-generating pores, monomer for porous dielectrics, process for preparing poly-o-hydroxyamides, process for preparing ploybenzoxazoles, and processes for producing an electronic component - Google Patents
Methods for producing a dielectric, dielectric having self-generating pores, monomer for porous dielectrics, process for preparing poly-o-hydroxyamides, process for preparing ploybenzoxazoles, and processes for producing an electronic component Download PDFInfo
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- US20060214139A1 US20060214139A1 US11/439,455 US43945506A US2006214139A1 US 20060214139 A1 US20060214139 A1 US 20060214139A1 US 43945506 A US43945506 A US 43945506A US 2006214139 A1 US2006214139 A1 US 2006214139A1
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- 238000000034 method Methods 0.000 title claims description 52
- 230000008569 process Effects 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000000178 monomer Substances 0.000 title claims description 14
- 239000003989 dielectric material Substances 0.000 title claims description 10
- 239000011148 porous material Substances 0.000 title abstract description 20
- 229920002577 polybenzoxazole Polymers 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims description 49
- 239000002904 solvent Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- -1 —CF((CF2)nCF3)2 Chemical group 0.000 claims description 25
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 24
- 125000005842 heteroatom Chemical group 0.000 claims description 21
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 21
- 239000004020 conductor Substances 0.000 claims description 20
- 125000006342 heptafluoro i-propyl group Chemical group FC(F)(F)C(F)(*)C(F)(F)F 0.000 claims description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229920006395 saturated elastomer Polymers 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910052717 sulfur Chemical group 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011593 sulfur Chemical group 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 4
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims 28
- 229930195733 hydrocarbon Natural products 0.000 claims 28
- 150000002430 hydrocarbons Chemical class 0.000 claims 28
- 238000001704 evaporation Methods 0.000 claims 2
- 238000000151 deposition Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 19
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 description 76
- 0 *C(=O)NC1=CC=C(*)C=C1O.*C1=CC=C2N=C(*)OC2=C1.[3HH].[OH-] Chemical compound *C(=O)NC1=CC=C(*)C=C1O.*C1=CC=C2N=C(*)OC2=C1.[3HH].[OH-] 0.000 description 37
- 238000003756 stirring Methods 0.000 description 28
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000011541 reaction mixture Substances 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 15
- 229910052710 silicon Inorganic materials 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000011261 inert gas Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000010703 silicon Substances 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 239000000725 suspension Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 238000007363 ring formation reaction Methods 0.000 description 10
- 238000010008 shearing Methods 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000002318 adhesion promoter Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 229910052581 Si3N4 Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 7
- 238000004528 spin coating Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 6
- RTYHOCUPZSSICM-UHFFFAOYSA-N C.C.C.C.CCC(=O)CC(=O)NCNC(=O)CC(C)=O.CCNC(C)(C)NC(=O)CC(=O)NCNC(=O)CC(C)=O Chemical compound C.C.C.C.CCC(=O)CC(=O)NCNC(=O)CC(C)=O.CCNC(C)(C)NC(=O)CC(=O)NCNC(=O)CC(C)=O RTYHOCUPZSSICM-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- SIPGOSZQFAZGDJ-UHFFFAOYSA-N C.C.C.C.C.C.C.C.CCC1=NC2(C1)CC(CC1=NC3(CC(CC(C)=O)=N3)C1)=N2.CCCC1=NC2(C1)CC(CC(C)=O)=N2 Chemical compound C.C.C.C.C.C.C.C.CCC1=NC2(C1)CC(CC1=NC3(CC(CC(C)=O)=N3)C1)=N2.CCCC1=NC2(C1)CC(CC(C)=O)=N2 SIPGOSZQFAZGDJ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- SESHFHJFJQEEMO-UHFFFAOYSA-N [1-(2-acetyloxy-3-aminonaphthalen-1-yl)-3-aminonaphthalen-2-yl] acetate Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC(N)=C3OC(=O)C)=C(OC(C)=O)C(N)=CC2=C1 SESHFHJFJQEEMO-UHFFFAOYSA-N 0.000 description 3
- 239000000370 acceptor Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002828 nitro derivatives Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- QDBOAKPEXMMQFO-UHFFFAOYSA-N 4-(4-carbonochloridoylphenyl)benzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=C(C(Cl)=O)C=C1 QDBOAKPEXMMQFO-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- IRDWCKNYHZPZHJ-UHFFFAOYSA-N [1-(2-acetyloxy-3-nitronaphthalen-1-yl)-3-nitronaphthalen-2-yl] acetate Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC(=C3OC(=O)C)[N+]([O-])=O)=C(OC(C)=O)C([N+]([O-])=O)=CC2=C1 IRDWCKNYHZPZHJ-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002717 polyvinylpyridine Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- KZZNMIMGMUSNMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene-2,3-diol Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=C(C=3O)O)=CC=CC2=C1 KZZNMIMGMUSNMW-UHFFFAOYSA-N 0.000 description 1
- AVVMKJFTELFQQH-UHFFFAOYSA-N 3-fluoro-2-[(2-nitrophenyl)methoxy]phenol Chemical compound OC1=CC=CC(F)=C1OCC1=CC=CC=C1[N+]([O-])=O AVVMKJFTELFQQH-UHFFFAOYSA-N 0.000 description 1
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 1
- 229910016570 AlCu Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VMWFICWZLXGZFM-UHFFFAOYSA-N C.C.C=C(C)C(=O)OC[Si](OC)(OC)OC.C=CC.C=CCNCCC[Si](OC)(OC)OC.CO[Si](CCC1=CC=CC=C1)(OC)OC.CO[Si](CCCN(C)CCO)(OC)OC.CO[Si](CCCNCCN)(OC)OC.CO[Si](CCCOCC1CO1)(OC)OC Chemical compound C.C.C=C(C)C(=O)OC[Si](OC)(OC)OC.C=CC.C=CCNCCC[Si](OC)(OC)OC.CO[Si](CCC1=CC=CC=C1)(OC)OC.CO[Si](CCCN(C)CCO)(OC)OC.CO[Si](CCCNCCN)(OC)OC.CO[Si](CCCOCC1CO1)(OC)OC VMWFICWZLXGZFM-UHFFFAOYSA-N 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N C=C(C)C(=O)Cl Chemical compound C=C(C)C(=O)Cl VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- UZQQNHVECQJKNW-UHFFFAOYSA-N C=CCOC1=CC(C(=O)Cl)=CC(C(=O)Cl)=C1 Chemical compound C=CCOC1=CC(C(=O)Cl)=CC(C(=O)Cl)=C1 UZQQNHVECQJKNW-UHFFFAOYSA-N 0.000 description 1
- AXABSIJWBIWMCS-UHFFFAOYSA-N CC(=O)OCC1=CC=CC=C1.CCC.CCC1=CC=CC=C1.CCOC(C)=O.[H]C Chemical compound CC(=O)OCC1=CC=CC=C1.CCC.CCC1=CC=CC=C1.CCOC(C)=O.[H]C AXABSIJWBIWMCS-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NLGOBIIKXFNGQR-UHFFFAOYSA-N NC1=CC(C2(C3=CC(N)=C(O)C=C3)C3=C(C=CC=C3)C3=C2C=CC=C3)=CC=C1O Chemical compound NC1=CC(C2(C3=CC(N)=C(O)C=C3)C3=C(C=CC=C3)C3=C2C=CC=C3)=CC=C1O NLGOBIIKXFNGQR-UHFFFAOYSA-N 0.000 description 1
- BXRBMOOAFJKBGL-UHFFFAOYSA-N NC1=CC2=CC=CC=C2C(C2=C3C=CC=CC3=CC(N)=C2O)=C1O Chemical compound NC1=CC2=CC=CC=C2C(C2=C3C=CC=CC3=CC(N)=C2O)=C1O BXRBMOOAFJKBGL-UHFFFAOYSA-N 0.000 description 1
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N NC1=CC=C(C2=CC(O)=C(N)C=C2)C=C1O Chemical compound NC1=CC=C(C2=CC(O)=C(N)C=C2)C=C1O ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 1
- NJYWFNOYGBIESN-UHFFFAOYSA-N NC1=CC=C(OC2=C(C3=C4C=CC=CC4=CC=C3OC3=CC(O)=C(N)C=C3)C3=CC=CC=C3C=C2)C=C1O Chemical compound NC1=CC=C(OC2=C(C3=C4C=CC=CC4=CC=C3OC3=CC(O)=C(N)C=C3)C3=CC=CC=C3C=C2)C=C1O NJYWFNOYGBIESN-UHFFFAOYSA-N 0.000 description 1
- HXXUQHDRWXWIBO-UHFFFAOYSA-N N[NH+](C1C(C2)C=CC2C1)[O-] Chemical compound N[NH+](C1C(C2)C=CC2C1)[O-] HXXUQHDRWXWIBO-UHFFFAOYSA-N 0.000 description 1
- NJXJIORLTDUCML-UHFFFAOYSA-N N[NH+](c(cc1)cc(cc2)c1cc2[NH+](N)[O-])[O-] Chemical compound N[NH+](c(cc1)cc(cc2)c1cc2[NH+](N)[O-])[O-] NJXJIORLTDUCML-UHFFFAOYSA-N 0.000 description 1
- MPLIKDBXWSLPFZ-UHFFFAOYSA-N O=C(Cl)C1=CC(C#CC2=CC=CC=C2)=CC(C(=O)Cl)=C1 Chemical compound O=C(Cl)C1=CC(C#CC2=CC=CC=C2)=CC(C(=O)Cl)=C1 MPLIKDBXWSLPFZ-UHFFFAOYSA-N 0.000 description 1
- OSUWBBMPVXVSOA-UHFFFAOYSA-N O=C(Cl)C1=CC=C(OC2=CC=C(C(=O)Cl)C=C2)C=C1 Chemical compound O=C(Cl)C1=CC=C(OC2=CC=C(C(=O)Cl)C=C2)C=C1 OSUWBBMPVXVSOA-UHFFFAOYSA-N 0.000 description 1
- NZZGQZMNFCTNAM-UHFFFAOYSA-N O=C(Cl)C1=CC=C2C=C(C(=O)Cl)C=CC2=C1 Chemical compound O=C(Cl)C1=CC=C2C=C(C(=O)Cl)C=CC2=C1 NZZGQZMNFCTNAM-UHFFFAOYSA-N 0.000 description 1
- HXYXVFUUHSZSNV-UHFFFAOYSA-N O=C(Cl)C1CC2C=CC1C2 Chemical compound O=C(Cl)C1CC2C=CC1C2 HXYXVFUUHSZSNV-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- HAYKPKAJUBHHHQ-UHFFFAOYSA-N [1-(2-acetyloxy-3-aminonaphthalen-1-yl)-3-aminonaphthalen-2-yl] acetate;hydrochloride Chemical compound Cl.C1=CC=C2C(C3=C4C=CC=CC4=CC(N)=C3OC(=O)C)=C(OC(C)=O)C(N)=CC2=C1 HAYKPKAJUBHHHQ-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical group CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011045 prefiltration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Images
Classifications
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
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- H01L21/02107—Forming insulating materials on a substrate
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- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
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- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
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- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02304—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment formation of intermediate layers, e.g. buffer layers, layers to improve adhesion, lattice match or diffusion barriers
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- 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
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- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
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- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
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- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
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- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
Definitions
- the invention relates to poly-o-hydroxyamides, a process for their preparation, polybenzoxazoles, and a process for their preparation, monomers for the preparation of the poly-o-hydroxyamides, an electronic component that contains the polybenzoxazoles as a dielectric, and a process for the production of such electronic components.
- the signal transit time in microchips depends both on the material of the conductor track and on the dielectric that is disposed between the conductor tracks. The lower the dielectric constant of the dielectric, the shorter too is the signal transit time.
- the dielectrics used to date are based on silica and have a dielectric constant of about four (4). These materials are gradually being replaced by organic dielectrics that have a substantially lower dielectric constant. The dielectric constant of these materials is generally below three (3).
- the conductor tracks preferably are formed from aluminum, AlCu, or AlCuSi.
- copper As conductor track material, owing to its lower electrical resistance in comparison with aluminum. Copper permits shorter signal transit time and hence a reduction in the conductor track cross section.
- the dielectric is first structured. The resulting trenches are first coated with a very thin barrier that is composed, for example, of titanium, titanium nitride, tantalum, tantalum nitride, silicon carbide, silicon nitride, or silicon carbonitride.
- the trenches are then first filled with copper and then excess copper is ground off mechanically.
- the dielectric must therefore be stable to the materials used for the grinding and must have sufficient adhesion to the substrate in order to avoid becoming detached during the mechanical grinding process.
- the dielectrics must also have sufficient stability in the following process steps in which further components of the microchips are produced. For this purpose, they must, for example, have sufficient thermal stability and must not undergo decomposition even at temperatures of more than 400° C.
- the dielectric must be stable to process chemicals, such as solvents, strippers, bases, acids or aggressive gases. Further requirements are good solubility and a sufficient shelf-life of the intermediates from which the dielectrics are produced.
- porous materials are currently being investigated in more detail. Owing to the air-filled nanopores, the dielectric constant decreases to values of two (2) or less.
- the porosity of the materials must not be chosen too high because their mechanical stability otherwise greatly decreases and the dielectric does not withstand mechanical loads as occur in chemical mechanical planarization (CMP).
- CMP chemical mechanical planarization
- the processing of the currently available porous dielectric is very difficult because both the process conditions and the solvent used have a great influence on pore size and pore size distribution. In most cases, the production of pores is effected by thermal decomposition reactions that have to be very exactly controlled. The decomposition products enter the air or ovens and, in addition to soiling and damaging the apparatuses, can also constitute a health hazard.
- U.S. Pat. No. 5,776,990 to Hedrick, et al. describes a porous polymer having a mean pore size of less than 100 nm.
- the copolymer is formed from thermally stable and thermally labile blocks. If a film of such a polymer is heated above the decomposition temperature of the labile block, a porous dielectric forms. In order to obtain the desired pore size, however, exact control of the process conditions is required, such as the sequence of temperature steps or the solvent used. Furthermore, gaseous byproducts that can soil or damage the apparatuses used and that are hazardous to health form.
- Polybenzoxazoles are polymers that have very high heat stability. The substances are already used for the production of protective and insulating layers. Polybenzoxazoles can be prepared by cyclization of poly-o-hydroxyamides. The poly-o-hydroxyamides have good solubility in organic solvents and good film formation properties. They can easily be applied to electronic components by using the spin coating technique. After a thermal treatment in which the poly-o-hydroxyamide is cyclicized to give the polybenzoxazole, a polymer that has the desired properties is obtained. Polybenzoxazoles can also be processed directly in their cyclized form. In this case, however, there are as a rule difficulties with the solubility of the polymer. Building blocks of poly-o-hydroxyamides are described, for example, in commonly-owned German Patent Application DE 100 11 608, which corresponds to U.S. Pat. No. 6,531,632 B2.
- E 1 and E 2 in each case independently, are hydrogen, a hydroxyl group or a saturated or unsaturated monovalent hydrocarbon substituents that may also contain one or more hetero atoms;
- Y 1 and Y 2 in each case independently for each position, are a divalent hydrocarbon substituent which may also contain one or more hetero atoms;
- Z 1 in each case independently for each position, is a structural unit of the Formula IIa or IIb in which the bond (-*) and the substituent -GR 5 are configured in the ortho position relative to one another,
- Z 2 in each case independently for each position, is a tetravalent hydrocarbon substituent which is composed of alkyl and/or aryl substituents linked to one another and may also include one or more hetero atoms;
- R 1 , R 2 , R 3 , and R 4 in each case independently, are H, —C 6 H 5 , —(CH 2 ) n —CH 3 , -G-(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 2 , -G-CH(CH 3 ) 2 , —C(CH 3 ) 3 , -G-C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , -G-(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —N(CH 3 ) 2 , —N(CF 3 ) 2 , —N(CF 3 ) 2 ,
- R 5 in each case independently, is H, —CO(CH 2 ) n —CH 3 , —COO—(CH 2 ) n —CH 3 , —(CH 2 ) n —CH 3 , —CH((CH 2 ) n CH 3 ) 2 , —CH(CH 3 ) 2 , —C(CH 3 ) 3 , —(CF 2 ) n —CF 3 , —CF((CF 2 ) n CF 3 ) 2 , —CF(CF 3 ) 2 , —C(CF 3 ) 3 , —(CH 2 ) n -C 6 H 5 , —COO—(CH 2 ) n —C 6 H 5 ,
- G is oxygen or sulfur
- a 0 or 1
- b has a value of from 1 to 200
- c has a value of from 0 to 200
- d 0 or 1
- n is an integer from 0 to 10.
- the poly-o-hydroxyamides of the Formula I form, on cyclization to give the polybenzoxazole, pores having a magnitude of a few ten nanometers without it being necessary to provide a component, for example a thermally labile block or an additive, in the polymer material.
- the pore size is influenced primarily by the structure of the poly-o-hydroxyamide of the Formula I and only to a small extent by the process conditions, i.e. the solvent used and the temperature program. It is not necessary to provide additional components that are decomposed to give gaseous products, in order to produce pores. Consequently, during pore formation, no impurities form and no damage is done to the microchip structures already produced.
- the polybenzoxazoles obtained After the cyclization, the polybenzoxazoles obtained have dielectric constants of less than 2.5, owing to the porosity of the material, which corresponds to the lower limit of the fluorine-free polybenzoxazoles having high thermal stability.
- the polybenzoxazoles have high stability to chemicals as used in the production of microchips, such as solvents, strippers, bases, acids, or aggressive gases.
- the polymer materials are therefore very suitable for microelectronic applications. Moreover, the materials are also outstandingly suitable for the copper damascene technique. During the copper grinding process, no disadvantageous effects occur, such as delamination, cracking or blister formation.
- the poly-o-hydroxyamides of the Formula I, according to the invention are very readily soluble in many organic solvents. Solvents that may be used are, for example, acetone, cyclohexanone, diethylene glycol monoethyl or diethyl ether, N-methylpyrrolidone, y-butyrolactone, ethyl lactate, methoxypropyl acetate, tetrahydrofuran, ethyl acetate and mixtures of said solvents.
- the solutions can be very readily applied to surfaces of electronic components e.g. by spin coating, spraying or dip methods and have a very good film quality. Trenches having a width of less than 100 nm and an aspect ratio of >4 can also be filled without difficulties.
- the poly-o-hydroxyamides according to the invention can be cyclized by heating to temperatures of 200 to 500° C. Apart from the desired pore formation, there is no formation of defects, such as cracks in the filled trenches.
- the poly-o-hydroxyamides of the Formula I are prepared from bis-o-aminophenols and dicarboxylic acids or their derivatives.
- the substituents derived from the dicarboxylic acids can have a wide variety of structures. They may include saturated, unsaturated or aromatic hydrocarbon substituents, combinations of these substituents also being possible. Saturated substituents may be straight-chain or branched. Furthermore, one or more carbon atoms may also be replaced by heteroatoms, or the substituents Y 1 and Y 2 may also have groups formed from a plurality of heteroatoms. Heteroatoms are understood here as meaning atoms which are not carbon or hydrogen. Particularly preferred heteroatoms are O, N, S, Si, and P.
- the chain length determined by the indices a, b, c, and d can be controlled by the reaction conditions, for example by using the rate of addition of the starting materials or by controlling the temperature at which the reaction is performed.
- a distribution of chain lengths is obtained in such a polymerization, the reaction being carried out in such a way that the average chain length is within the range of values indicated above for the indices a, b, c, and d.
- a narrow molecular weight distribution of the polymers is desirable.
- the reaction is controlled in such a way that values in the range of 1 to 200, preferably 4 to 80, result.
- the reaction is performed in such a way that values in the range of 0 to 200, preferably 0 to 50, result.
- the molecular weights or averaged chain lengths can be determined by customary methods, e.g. gel permeation chromatography (GPC).
- the properties of the polymer are substantially determined by the group Z 1 .
- the substituents R 1 , R 2 , R 3 , and R 4 are particularly preferably hydrogen atoms and the substituents GR 5 are particularly preferably a hydroxyl group or acetyl group.
- These groups Z 1 permit cyclization to give the benzoxazole under comparatively mild conditions.
- Particularly preferred structures for the group Z 1 (formulae IIa and IIb) are shown below:
- the polymer may also include further groups Z 2 which do not include any binaphthyl substituents.
- the groups Z 2 may have a very varied range of structures.
- the groups Z 2 preferably include 6 to 30 carbon atoms.
- the group Z 2 preferably includes one or two phenyl groups on which the group GR 5 and the nitrogen atom continuing the polymer chain are bonded.
- the group GR 5 and the nitrogen atom are preferably disposed in the ortho position relative to one another in order also to permit cyclization to give the oxazole in the case the groups Z 2 .
- the part-structures of the group Z 2 in particular phenyl groups, which carry the groups GR 5 can be linked via alkylene and/or arylene groups or via groups formed from hetero atoms.
- the groups Z 2 can be substituted by monovalent groups, in particular alkyl groups.
- Z 2 is a structural unit which is selected from the group: in which R 6 is a divalent substituent that is selected from the following group: in which
- R 7 is an alkyl substituent having 1 to 10 carbon atoms or an aryl substituent having 5 to 22 carbon atoms;
- e is an integer from 1 to 10.
- G in groups Z 1 and Z 2 is preferably an oxygen atom.
- substituents R 5 the following substituents are particularly preferred: in which m is an integer from 0 to 10, in particular from 0 to 5.
- the groups Y 1 and Y 2 may likewise have a very large variety of structures and preferably include 5 to 30 carbon atoms.
- the groups Y 1 and Y 2 may include saturated and unsaturated hydrocarbon groups as part-structures, aromatic hydrocarbon groups being preferred.
- f is an integer from 1 to 10;
- g is an integer from 1 to 10.
- Poly-o-hydroxyamide of the Formula I may carry, as terminal groups E 1 and E 2 , a hydrogen atom or a hydroxyl group or a saturated or unsaturated monovalent hydrocarbon substituent which may also contain one or more hetero atoms.
- the hydrocarbon substituent preferably includes 1 to 30 carbon atoms.
- E 1 and E 2 are preferably selected from the following group:
- h 0-10
- q is *—O—*, *—S—*, or *—NH—*.
- terminal groups E 1 and E 2 can be introduced into the poly-o-hydroxyamides of the Formula I by corresponding active precursors, for example acid chlorides.
- the polybenzoxazoles obtained from the poly-o-hydroxyamides of the Formula I by cyclization have advantageous properties with respect to the thermal stability, the mechanical strength and the electrical insulating effect.
- the invention therefore also relates to polybenzoxazoles of the Formula III in which and a, b, c, d, R 1 , R 2 , R 3 , R 4 , R 5 , Y 1 , Y 2 , E 1 , E 2 , and G have the meaning stated in the case of Formula I.
- the structures of the groups shown in the Formula III are equally applicable to both classes of compounds.
- Formula III represents a polymer having a continuous polymer backbone. For reasons of simplicity, however, the molecule in Formula III has been shown in two parts.
- the poly-o-hydroxyamides of Formula I can be prepared by reacting bis-o-aminophenols or bis-o-aminothiophenols with dicarboxylic acids or their activated derivatives.
- the invention therefore also relates to monomers of the Formulae IVa and IVb: in which R 1 , R 2 , R 3 , R 4 , R 5 , and G have the meanings stated in the case of Formula I.
- the monomers of the Formulae IVa and IVb are prepared by customary synthesis processes, as described, for example, in Organikum, Wiley-VCH, 1999, page 228 et seq., page 324 et seq. and page 340 et seq. Similar monomers are described, for example, in U.S. Pat. No 4,525,539 or in European Patent No. EP 0 317 942.
- the monomers of the Formulae IVa and IVb can be reacted with dicarboxylic acids or their activated derivatives to give the desired poly-o-hydroxyamides of the Formula I.
- the invention therefore also relates to a process for the preparation of poly-o-hydroxyamides of the Formula I, monomers of the Formula IVa and/or IVb being reacted with a dicarboxylic acid or an activated dicarboxylic acid derivative of the Formulae Va and/or Vb.
- L is a hydroxyl group or an activating group
- Y 1 and Y 2 have the meaning stated in the case of Formula I.
- acid chlorides or activated esters for example sulfonic acid esters
- dicarboxylic acid derivatives of the formula V can be used as an activating group for the dicarboxylic acid derivatives of the formula V.
- the reaction of the monomers of the Formula IVa or IVb and of the dicarboxylic acids of the Formulae Va and Vb can, however, also be effected in the presence of a compound that activates the carboxylic acid, such as, for example, carbonyldiimidazole or dicyclohexylcarbodiimide.
- a compound that activates the carboxylic acid such as, for example, carbonyldiimidazole or dicyclohexylcarbodiimide.
- all reagents which bind the water formed in the reaction to themselves are suitable.
- the monomers of the Formula IVa or IVb and the dicarboxylic acid(s) or optionally the dicarboxylic acid derivatives of the Formula Va or Vb are reacted in an organic solvent at ⁇ 20 to 150° C. in the course of 5 to 20 hours.
- terminal groups of the polymer can be blocked with a suitable reagent in order thus to introduce the terminal groups E 1 and E 2 .
- Suitable-reagents have already been described in the explanation of the compounds of the Formula I.
- the poly-o-hydroxyamide of the formula I which has formed after the reaction is precipitated by dropwise addition of the reaction solution to a precipitating agent, washed and dried.
- Suitable precipitating agents are water and alcohols, such as isopropanol, butanol, or ethanol. Mixtures of these precipitating agents may also be used. It is also suitable for the precipitating agent to contain from 0.1% to 10% of ammonia. After filtration and drying, the precipitated polymer can be directly further processed and, for example for application to a semiconductor substrate, can be dissolved in one of the solvents mentioned further above.
- the polymerization to give the poly-o-hydroxyamide of the Formula I can be carried out in the presence of a base in order to trap acid liberated.
- Suitable basic acid acceptors are, for example, pyridine, triethylamine, diazabicyclooctane, or polyvinylpyridine. However, other basic acid acceptors may also be used.
- Compounds that are readily soluble in the solvent used for the synthesis for example N-methylpyrrolidone, and in the precipitating agent, for example water or water/alcohol mixtures, are those that are completely insoluble in the solvent, such as, for example, crosslinked polyvinylpyridine, are particularly preferred.
- the acid acceptors can then easily be separated from the resulting poly-o-hydroxyamide during the working up of the reaction product.
- Particularly suitable solvents for the polymer synthesis are ⁇ -butyrolactone, tetrahydrofuran, N-methylpyrrolidone, and dimethylacetamide.
- any solvent in which the starting components are readily soluble can in principle be used.
- the invention furthermore relates to a process for the preparation of polybenzoxazoles of the Formula III, poly-o-hydroxyamides of the Formula I being heated. Heating results in the formation of an oxazole ring or thiazole ring with elimination of a small molecule, in general water, the polybenzoxazoles of the Formula III, according to the invention, being obtained.
- the pore formation that occurs is influenced only to a slight extent by the reaction conditions.
- the pores have a diameter in the region of a few ten nanometers and a narrow pore distribution. The process therefore permits large tolerances in the production of the dielectric, which substantially simplifies the reaction procedure.
- the polybenzoxazole of Formula III which is prepared by the process according to the invention, has a very low dielectric constant of k ⁇ 2.5, owing to the pores enclosed in the dielectric. It adheres very well to surfaces relevant to chip technology, such as silicon, silicon carbide, silicon carbonitride, silicon nitride, silica, titanium, tantalum, titanium nitride, tantalum nitride, or silicon oxynitride.
- the invention therefore also relates to an electronic component that contains the polybenzoxazole of Formula III described above.
- Polybenzoxazole of Formula III may be disposed, for example, as a dielectric between conductor tracks or conductor track planes or as a buffer layer between the microchip and the housing surrounding it.
- the dielectrics according to the invention are outstandingly suitable for the copper damascene technique. During the grinding process, no disadvantageous effects, such as delamination, cracking or blister formation, occur.
- the invention therefore also relates to a process for the production of an electronic component, a solution of a poly-o-hydroxyamide of the Formula I in a solvent first being prepared. This solution is applied to a substrate and the solvent is evaporated so that a film is obtained. The film is then heated in order to cyclize the poly-o-hydroxyamide and convert it into the polybenzoxazole of Formula III. The film is then structured in order to obtain a resist structure which has trenches. A conductive material, for example copper, is then deposited on the resist structure so that the trenches are filled with a conductive material. Finally, excess conductive material is removed.
- a conductive material for example copper
- lithographic processes can be used for structuring the polybenzoxazole film, an etch-resistant mask being produced on the film.
- the structure of the mask is then transferred into the film of the polybenzoxazole according to the invention by etching.
- Copper is preferably used as conductive material.
- a barrier can be provided between dielectric and conductive material.
- the materials already mentioned further above are suitable as material for the barrier. Excess conductive material is removed, for example, by chemical mechanical planarization.
- the invention furthermore relates to a process for the production of an electronic component, a solution of a poly-o-hydroxyamide of Formula I described above first being prepared in a solvent. The solution is then applied to a substrate that already has on its surface metallic structures between which trenches are formed. Such structures are, for example, conductor tracks. The solvent is evaporated so that the trenches are filled with the poly-o-hydroxyamide. Finally, the substrate is heated in order to cyclize the poly-o-hydroxyamide to give a polybenzoxazole.
- adhesion of the polyhydroxyamides to surfaces relevant in microelectronics can be improved by adding adhesion promoters.
- FIG. 1 is a partial diagrammatic and partial schematic drawing showing a setup according to the invention for determining an dielectric constant
- FIG. 2 is a photograph showing a shadow mask as used in example 25 for the production of electrodes.
- the corresponding bishydroxybinaphthyl and 3-fluoro-6-nitrobenzyloxyphenol are initially introduced under inert gas (nitrogen or argon) into a three-necked flask that is provided with a stirrer and an inert gas connection, and N,N-dimethylformamide is added to these at room temperature.
- the mixture is stirred for about 10 to 20 minutes at room temperature.
- potassium carbonate is added in portions to the solution under inert gas.
- the solution is stirred at an elevated temperature for a few hours.
- the reaction temperature is suitably chosen from 60 to 140° C. The reaction occurs over course of 1 to 10 hours.
- N,N-dimethylformamide for example, N-methylpyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone, or dimethylacetamide can also be used.
- concentrations of the starting materials are suitably chosen in a range from 5 to 50% by weight.
- the suspension formed is cooled to room temperature and poured into a cooled (2-10° C.), aqueous potassium hydroxide solution.
- the product is precipitated in crystalline form. The precipitation can be accelerated by adding ethyl acetate.
- the product is filtered, washed with water, and then added to a 10% strength solution of acetic acid in water.
- the solution is stirred for 15 to 30 minutes, filtered, washed with water and dried under inert gas at 40° C./100 mbar in a drying oven until the weight remains constant.
- the crude product obtained in this manner is recrystallized from a solution in tetrahydrofuran and petroleum ether and dried again under reduced pressure.
- the hydrogenation is effected by known hydrogenation processes for nitro compounds, as described, for example, in European Patent No. EP 905 121, example 8.
- the nitro compound obtained in stage 1 can be dissolved, for example, in tetrahydrofuran, palladium on active carbon added and hydrogenation effected with hydrogen at superatmospheric pressure in an autoclave.
- the bis((3-benzyloxy-4-nitro)phenoxy)binaphthyl prepared in stage 1 is dissolved in tetrahdyrofuran, and palladium on active carbon is added under inert gas.
- the amount of Pd/C is about 10% of the amount of the compound to be hydrogenated.
- the suspension is introduced into a previously heated hydrogenation reactor under argon inert gas and hydrogenated with hydrogen at room temperature under pressure.
- the hydrogenation time is in general 10 to 50 hours.
- the hydrogen pressure is suitably chosen from 0.5 to 5 bar.
- the concentration of the compound to be hydrogenated in tetrahydrofuran is 5 to 30% by weight.
- tetrahydrofuran for example, dioxane, halogenated hydrocarbons or toluene can also be used as the solvent.
- the suspension is transferred under inert gas into pure ethanol, and concentrated hydrochloric acid is added with stirring until a clear solution forms.
- the solution is filtered over a Bütchner funnel in order to remove the Pd catalyst. Thereafter, about 70% of the amount of solvent is distilled off under reduced pressure and the concentrated solution is added to a solution of diethyl ether and acetone (volume ratio 7:3) with rapid stirring. During this procedure, the product is precipitated in crystalline form.
- the suspension is stored for 12-24 hours at 0° C. to 18° C. The product is then filtered off with suction and dried.
- the aminophenol is present as the hydrochloride. In contrast to the free aminophenol the form is not so greatly sensitive to oxidation by atmospheric oxygen.
- Moistened silica is initially introduced into a three-necked flask provided with a stirrer, a reflux condenser and an inert gas connection, and 10% strength sulfuric acid is added.
- the ratios are chosen at about 10 parts by weight of silica per 6 parts by weight of 10% strength sulfuric acid.
- 200 parts by weight of dichloromethane and 10 parts by weight of dihydroxybinaphthyl are then added in this sequence.
- About 10 parts by weight of 65% strength nitric acid are then added at a temperature of 2 to 10° C. in the course of 15 to 60 minutes. After the end of the addition, the suspension is stirred until quantitative conversion of the starting material at room temperature.
- the abovementioned ratio can be changed in a range of up to about 20%.
- dichloromethane other halogenated hydrocarbons may also be used as the solvent.
- the suspension is filtered.
- the product which is present adsorbed onto the SiO 2 surface, is dissolved in a suitable solvent, such as, for example, acetone or ethyl acetate, and filtered. This procedure is repeated twice. The organic fractions are combined and evaporated down. The concentrated solution is slowly poured into dimethyl ether while stirring, and the precipitated product is filtered off with suction. The product is then dried under inert gas at 40° C./100 mbar in a drying oven until the weight remains constant.
- the crude product is dissolved in toluene at room temperature (2 ml/g) and heated to 90° C. and petroleum ether (4 ml/g) is added until crystallization begins. Thereafter, the suspension is slowly cooled to room temperature, and the suspension is stored for a further 4 h in a freezer at ⁇ 18° C. and then filtered. The product obtained is dried for 24 h at 200 mbar and 55° C.
- the hydrogenation is effected according to known processes for the hydrogenation of nitro compounds, as described, for example, in European Patent No. EP 905 121, example 8.
- the suspension is then transferred under inert gas into 200 ml of ethanol. 10 ml of concentrated HCl are added with stirring and, when the product has completely dissolved, filtration is effected three times over a Büchner funnel to remove the Pd catalyst.
- the solution thus obtained is evaporated down to about 20 ml of ethanol at 70° C. and 300 mbar and then added to a solution of 700 ml of diethyl ether and 30 ml of acetone with rapid stirring.
- the suspension is stored for 24 h at ⁇ 18° C. and the solid is filtered off and dried.
- Endcaps (E 1 , E 2 ):
- reaction solution is cooled to 10° C., after which 19.76 g (0.25 mol) of pyridine, dissolved in 30 ml of distilled ⁇ -BL, are added to said reaction solution and the latter is warmed up to room temperature and stirred for 2 hours.
- the reaction mixture is filtered and the filtrate is added dropwise to a mixture of 1 1 of demineralized water and 200 ml of isopropanol while stirring, a further 3 l of demineralized water being added during the dropwise addition.
- the precipitated polymer is filtered off with suction and washed with 2 l of cold demineralized water. After the filtration with suction, the polymer is stirred twice for 1 hour at room temperature in 2.5 portions of a 3% strength ammonia solution and then filtered off with suction. The polymer is washed neutral with demineralized water, filtered off, and dried for 72 hours at 50° C./10 mbar.
- the polymer prepared in this manner is readily soluble in solvents such as NMP, ⁇ -BL, cyclohexanone, cyclopentanone or mixtures thereof.
- reaction mixture is cooled to 10° C., after which 9.48 g (0.12 mol) of pyridine, dissolved in 30 ml of distilled ⁇ -BL, are added to said reaction mixture and the latter is warmed up to room temperature and stirred for 2 hour.
- Polymer 2 is isolated and worked-up analogously to example 4.
- Polymer 3 is isolated and worked-up analogously to example 4.
- reaction mixture is cooled to 10° C., after which 19.76 g (0.25 mol) of pyridine, dissolved in 50 ml of distilled ⁇ -BL, are added and said reaction mixture is warmed up to room temperature and stirred for 2 hours.
- Polymer 4 is isolated and worked-up analogously to example 4.
- reaction mixture is cooled to 10° C., after which 19.76 g (0.25 mol) of pyridine, dissolved in 50 ml of distilled ⁇ -BL, were added and said reaction mixture is warmed up to room temperature and stirred for 2 hours.
- Polymer 6 is isolated and worked-up analogously to example 4.
- 25 g of the polymers described in examples 4 to 9 are dissolved in 75 g of distilled NMP or distilled ⁇ -BL.
- the dissolution process is expediently effected on a shaking apparatus at room temperature.
- the solution is then filtered under pressure through a 0.2 ⁇ m filter into a cleaned, particle-free glass sample tube.
- the viscosity of the polymer solution can be changed by varying the dissolved mass of polymer.
- adhesion promoter e.g. N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane
- the adhesion promoter should give a monomolecular layer on the surface of the parts to be adhesively bonded.
- the adhesion promoter can expediently be applied by the spin coating technique.
- the adhesion promoter solution is applied via a 0.2 ⁇ m prefilter to the surface to be adhesively bonded and is spun for 30 s at 5 000 rpm.
- a drying step is then effected for 60 s at 100° C.
- a processed silicon wafer that has lands and trenches up to a minimum dimension of, in each case, about 150 nm is coated, as described in example 10, with an adhesion promoter.
- the filtered solution of polymer 1, which was obtained according to example 11, is then applied to the wafer by using a syringe and is uniformly distributed using a spin coater. The spin coater speed is 2,000 rpm.
- the polymer is then heated on a hotplate for 1 min at 120° C. and for 2 min at 200° C.
- the coated wafer is then heated under nitrogen or argon in an oven to 425° C. for 60 min.
- the polybenzoxazole thus obtained is inert to acids, bases and organic solvents.
- a 4′′ silicon wafer is sputtered with a 50 nm thick titanium nitride layer.
- the solution prepared in example 11 is applied to this wafer by spin coating, at 500 rpm for 5 s and at 2,000 rpm for 25 s.
- 10 silicon chips having an edge length of 4 ⁇ 4 mm2, which had likewise been sputtered with a 50 nm thick titanium nitride layer are then pressed onto the polymer film with a force of 2 N.
- This stack is then heated in a nitrogen atmosphere for 1 h at 425° C. in an oven. Following cooling to room temperature, an adhesion test was carried out using a shear tester, Dage series 400.
- the mean value for polymer 1 that was required for shearing off the chips is 15.51 N/mm 2 .
- the experiment carried out was the same as that described in Example 14, but the surface of the wafer and of the chips was formed not of titanium nitride but of tantalum nitride.
- the mean value of the force for polymer 1 that was required for shearing off the chips is 16.01 N/mm 2 .
- the experiment carried out is the same as that described in Example 14, but the surface of the wafer and of the chips is formed not of titanium nitride but of silicon.
- the mean value of the force for polymer 1 that was required for shearing off the chips is 17.05 N/mm 2 .
- the experiment carried out is the same as that described in Example 14, but the surface of the wafer and of the chips is not formed of titanium nitride but of silicon nitride.
- the mean value of the force for polymer 1 that was required for shearing off the chips is 15.16 N/mm 2 .
- the experiment carried out is the same as that described in example 14, but the surface of the wafer and of the chips is formed not of titanium nitride but of silica.
- the mean value of the force for polymer 1 that was required for shearing off the chips is 16.20 N/mm 2 .
- the experiment carried out is the same as that described in Example 14, but the surface of the wafer and of the chips was not formed of titanium nitride but of silicon carbide.
- the mean value of the force for polymer 1 that was required for shearing off the chips is 15.73 N/mm 2 .
- the experiment carried out is the same as that described in Example 14, but the surface of the wafer and of the chips was not formed of titanium nitride but of tantalum.
- the mean value of the force for polymer 1 that was required for shearing off the chips is 16.68 N/mm 2 .
- the experiment carried out is the same as that described in example 14, but the surface of the wafer and of the chips were formed not of titanium nitride but of titanium.
- the mean value of the force for polymer 1 that was required for shearing off the chips is 15.84 N/mm 2 .
- the experiment carried out is the same as that described in Example 14, but the surface of the wafer and of the chips was not formed of titanium nitride but of polyimide.
- the mean value of the force for polymer 1 that was required for shearing off the chips is 16.26 N/mm 2 .
- a polymer was prepared analogously to Example 1 of U.S. Pat. No. 5,077,378 and a polymer solution in NMP was prepared as described in Example 11. The adhesion of the polymer was then determined as described in examples 14 to 22. The following mean values were found: TABLE 1 Adhesion of the comparative polymers Surface Force for shearing off (N/mm 2 ) Titanium nitride 14.71 Tantalum nitride 15.69 Silicon 15.21 Silicon nitride 14.03 Silica 14.94 Silicon carbide 13.37 Tantalum 13.96 Titanium 14.07 Polyimide 13.02
- the polymer 1 was applied from a 20% strength solution (solvent: NMP) to a 4′′ silicon wafer by spin coating, at 500 rpm for 5 s and at 2 000 rpm for 25 s. After a short softbake of 1 min at 120° C. and 2 min at 200° C. on a hotplate, the wafer is heated in a nitrogen atmosphere for 1 h at 400° C. in an oven. After cooling to room temperature, the coated wafer is heated in NMP to 80° C. for 5 h. Thereafter, the wafer is dried in vacuo for 60 min at 200° C. and the mass difference is determined.
- solvent solvent
- the decrease in mass is 0.8%.
- the dielectric constant was measured using the configuration shown in FIG. 1 .
- the polymer 1 was dissolved in NMP (25% strength solution) and the solution was filtered under pressure through a membrane having 0.2 ⁇ M pores.
- This solution was applied by spin coating to a substrate 1 on which a 600 nm thick titanium layer 2 is already present.
- the layer 3 is dried at 120° C. and 200° C., in each case for 2 min, on a hotplate and then heated at 430° C. for one hour in a nitrogen atmosphere. Titanium electrodes 4 are then sputtered onto this layer 3 by using a shadow mask shown in FIG. 2 .
- the shadow mask shown in FIG. 2 includes orifices 5 which correspond to the position of the titanium electrodes 4.
- the dielectric constant is determined using the impedance spectrometer 6 and is 2.31 in the frequency range from 100 Hz to 1 MHz.
- the dielectric constant was determined analogously to example 25 in polymers 2 to 5. The values found are shown in Table 2.
- a polymer was prepared analogously to Example 1 of U.S. Pat. No. 5,077,378 and the dielectric constant is determined as described in example 25. The value found is likewise shown in Table 2.
- TABLE 2 Dielectric constant of various polymers Example Polymer Dielectric constant 25 1 2.31 26 2 2.32 27 3 2.44 28 4 2.31 29 5 2.39 30 U.S. Pat. No. 5,077,378 Ex. 1 3.1
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Abstract
Poly-o-hydroxyamides include binaphthyl substituents as repeating units. The poly-o-hydroxyamides can be cyclized to give the polybenzoxazole by heating. Pore formation occurs, so that a dielectric having a very low dielectric constant k of less than 2.5 is obtained.
Description
- This is a divisional application of application Ser. No. 10/424,376, filed Apr. 28, 2003; the application also claims the priority, under 35 U.S.C. §119, of German patent application DE 102 18 788.6, filed Apr. 26, 2002; the prior applications are herewith incorporated by reference in their entirety.
- The invention relates to poly-o-hydroxyamides, a process for their preparation, polybenzoxazoles, and a process for their preparation, monomers for the preparation of the poly-o-hydroxyamides, an electronic component that contains the polybenzoxazoles as a dielectric, and a process for the production of such electronic components.
- In order to avoid cross-talk of signals which is caused by capacitive coupling, adjacent conductor tracks in microchips are insulated from one another by a dielectric disposed between the conductor tracks. Compounds that are to be used as a dielectric must meet various requirements. Thus, the signal transit time in microchips depends both on the material of the conductor track and on the dielectric that is disposed between the conductor tracks. The lower the dielectric constant of the dielectric, the shorter too is the signal transit time. The dielectrics used to date are based on silica and have a dielectric constant of about four (4). These materials are gradually being replaced by organic dielectrics that have a substantially lower dielectric constant. The dielectric constant of these materials is generally below three (3).
- In the microchips customary at present, the conductor tracks preferably are formed from aluminum, AlCu, or AlCuSi. With increasing integration density of the memory chips, there is a changeover to copper as conductor track material, owing to its lower electrical resistance in comparison with aluminum. Copper permits shorter signal transit time and hence a reduction in the conductor track cross section. In contrast to the techniques customary to date, in which the dielectric is introduced into the trenches between the conductor tracks, in the copper damascene technique, the dielectric is first structured. The resulting trenches are first coated with a very thin barrier that is composed, for example, of titanium, titanium nitride, tantalum, tantalum nitride, silicon carbide, silicon nitride, or silicon carbonitride. The trenches are then first filled with copper and then excess copper is ground off mechanically. The dielectric must therefore be stable to the materials used for the grinding and must have sufficient adhesion to the substrate in order to avoid becoming detached during the mechanical grinding process. Furthermore, the dielectrics must also have sufficient stability in the following process steps in which further components of the microchips are produced. For this purpose, they must, for example, have sufficient thermal stability and must not undergo decomposition even at temperatures of more than 400° C. Moreover, the dielectric must be stable to process chemicals, such as solvents, strippers, bases, acids or aggressive gases. Further requirements are good solubility and a sufficient shelf-life of the intermediates from which the dielectrics are produced.
- With unfluorinated polymers that have sufficient thermal stability, dielectric constants down to about 2.5 are obtainable. By fluorination of the polymers, it is true that the dielectric constant can be further reduced. However, these materials have poor adhesion to the substrate and, at high temperatures, eliminate fluorine-containing decomposition products, which may damage the chip.
- In order to be able to provide materials having a dielectric constant of <2.5, porous materials are currently being investigated in more detail. Owing to the air-filled nanopores, the dielectric constant decreases to values of two (2) or less. However, the porosity of the materials must not be chosen too high because their mechanical stability otherwise greatly decreases and the dielectric does not withstand mechanical loads as occur in chemical mechanical planarization (CMP). Furthermore, the processing of the currently available porous dielectric is very difficult because both the process conditions and the solvent used have a great influence on pore size and pore size distribution. In most cases, the production of pores is effected by thermal decomposition reactions that have to be very exactly controlled. The decomposition products enter the air or ovens and, in addition to soiling and damaging the apparatuses, can also constitute a health hazard.
- U.S. Pat. No. 5,776,990 to Hedrick, et al. describes a porous polymer having a mean pore size of less than 100 nm. The copolymer is formed from thermally stable and thermally labile blocks. If a film of such a polymer is heated above the decomposition temperature of the labile block, a porous dielectric forms. In order to obtain the desired pore size, however, exact control of the process conditions is required, such as the sequence of temperature steps or the solvent used. Furthermore, gaseous byproducts that can soil or damage the apparatuses used and that are hazardous to health form.
- Polybenzoxazoles (PBO) are polymers that have very high heat stability. The substances are already used for the production of protective and insulating layers. Polybenzoxazoles can be prepared by cyclization of poly-o-hydroxyamides. The poly-o-hydroxyamides have good solubility in organic solvents and good film formation properties. They can easily be applied to electronic components by using the spin coating technique. After a thermal treatment in which the poly-o-hydroxyamide is cyclicized to give the polybenzoxazole, a polymer that has the desired properties is obtained. Polybenzoxazoles can also be processed directly in their cyclized form. In this case, however, there are as a rule difficulties with the solubility of the polymer. Building blocks of poly-o-hydroxyamides are described, for example, in commonly-owned German Patent Application DE 100 11 608, which corresponds to U.S. Pat. No. 6,531,632 B2.
-
- Upon heating, the o-hydroxyamide undergoes cyclization to give the oxazole; water is liberated.
- It is accordingly an object of the invention to provide methods for producing a dielectric, a dielectric having self-generating pores, a monomer for porous dielectrics, a process for preparing poly-o-hydroxyamides, a process for preparing polybenzoxazoles, a processes for producing an electronic component, and a method for forming a dielectric that overcome the hereinafore-mentioned disadvantages of the heretofore-known devices of this general type and that provide and involve polymers that can be easily applied to electronic components and that have a good electrical insulating effect after their cyclization and exhibit sufficient thermal stability and very good adhesive and filling properties.
-
- E1 and E2, in each case independently, are hydrogen, a hydroxyl group or a saturated or unsaturated monovalent hydrocarbon substituents that may also contain one or more hetero atoms;
- Y1 and Y2, in each case independently for each position, are a divalent hydrocarbon substituent which may also contain one or more hetero atoms;
-
- Z2, in each case independently for each position, is a tetravalent hydrocarbon substituent which is composed of alkyl and/or aryl substituents linked to one another and may also include one or more hetero atoms;
- R1, R2, R3, and R4, in each case independently, are H, —C6H5, —(CH2)n—CH3, -G-(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)2, -G-CH(CH3)2, —C(CH3)3, -G-C(CH3)3, —(CF2)n—CF3, -G-(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —N(CH3)2, —N(CF3)2,
- R5, in each case independently, is H, —CO(CH2)n—CH3, —COO—(CH2)n—CH3, —(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)2, —C(CH3)3, —(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —(CH2)n-C6H5, —COO—(CH2)n—C6H5,
- G is oxygen or sulfur,
- a is 0 or 1,
- b has a value of from 1 to 200,
- c has a value of from 0 to 200,
- d is 0 or 1, and
- n is an integer from 0 to 10.
- For reasons of simplicity, both the poly-o-hydroxyamides (G=0) and the poly-o-thioamides (G=S) of the Formula I are referred to below as poly-o-hydroxyamides. Statements made in connection with the polymer groups described above apply in context to both classes of compounds. Formula I represents a polymer having a continuous polymer backbone. For reasons of simplicity, however, the molecule in Formula I was represented in two parts.
- The poly-o-hydroxyamides of the Formula I, according to the invention, form, on cyclization to give the polybenzoxazole, pores having a magnitude of a few ten nanometers without it being necessary to provide a component, for example a thermally labile block or an additive, in the polymer material. The pore size is influenced primarily by the structure of the poly-o-hydroxyamide of the Formula I and only to a small extent by the process conditions, i.e. the solvent used and the temperature program. It is not necessary to provide additional components that are decomposed to give gaseous products, in order to produce pores. Consequently, during pore formation, no impurities form and no damage is done to the microchip structures already produced. After the cyclization, the polybenzoxazoles obtained have dielectric constants of less than 2.5, owing to the porosity of the material, which corresponds to the lower limit of the fluorine-free polybenzoxazoles having high thermal stability. The adhesion of the polybenzoxazole prepared from the poly-o-hydroxyamide of the Formula I to surfaces relevant for chip technology, such as silicon, silicon carbide, silicon carbonitride, silicon nitride, silica, titanium, tantalum, titanium nitride, tantalum nitride or silicon oxynitride, is very good. Furthermore, the polybenzoxazoles have high stability to chemicals as used in the production of microchips, such as solvents, strippers, bases, acids, or aggressive gases. The polymer materials are therefore very suitable for microelectronic applications. Moreover, the materials are also outstandingly suitable for the copper damascene technique. During the copper grinding process, no disadvantageous effects occur, such as delamination, cracking or blister formation. The poly-o-hydroxyamides of the Formula I, according to the invention, are very readily soluble in many organic solvents. Solvents that may be used are, for example, acetone, cyclohexanone, diethylene glycol monoethyl or diethyl ether, N-methylpyrrolidone, y-butyrolactone, ethyl lactate, methoxypropyl acetate, tetrahydrofuran, ethyl acetate and mixtures of said solvents. The solutions can be very readily applied to surfaces of electronic components e.g. by spin coating, spraying or dip methods and have a very good film quality. Trenches having a width of less than 100 nm and an aspect ratio of >4 can also be filled without difficulties. The poly-o-hydroxyamides according to the invention can be cyclized by heating to temperatures of 200 to 500° C. Apart from the desired pore formation, there is no formation of defects, such as cracks in the filled trenches.
- The poly-o-hydroxyamides of the Formula I are prepared from bis-o-aminophenols and dicarboxylic acids or their derivatives. The substituents derived from the dicarboxylic acids can have a wide variety of structures. They may include saturated, unsaturated or aromatic hydrocarbon substituents, combinations of these substituents also being possible. Saturated substituents may be straight-chain or branched. Furthermore, one or more carbon atoms may also be replaced by heteroatoms, or the substituents Y1 and Y2 may also have groups formed from a plurality of heteroatoms. Heteroatoms are understood here as meaning atoms which are not carbon or hydrogen. Particularly preferred heteroatoms are O, N, S, Si, and P. The chain length determined by the indices a, b, c, and d can be controlled by the reaction conditions, for example by using the rate of addition of the starting materials or by controlling the temperature at which the reaction is performed. Of course, a distribution of chain lengths is obtained in such a polymerization, the reaction being carried out in such a way that the average chain length is within the range of values indicated above for the indices a, b, c, and d. A narrow molecular weight distribution of the polymers is desirable. For the index b, the reaction is controlled in such a way that values in the range of 1 to 200, preferably 4 to 80, result. For the index c, the reaction is performed in such a way that values in the range of 0 to 200, preferably 0 to 50, result. The molecular weights or averaged chain lengths can be determined by customary methods, e.g. gel permeation chromatography (GPC).
- The properties of the polymer are substantially determined by the group Z1. In the group Z1, the substituents R1, R2, R3, and R4 are particularly preferably hydrogen atoms and the substituents GR5 are particularly preferably a hydroxyl group or acetyl group. These groups Z1 permit cyclization to give the benzoxazole under comparatively mild conditions. Particularly preferred structures for the group Z1 (formulae IIa and IIb) are shown below:
- In addition to the groups Z1, the polymer may also include further groups Z2 which do not include any binaphthyl substituents. The groups Z2 may have a very varied range of structures. The groups Z2 preferably include 6 to 30 carbon atoms. The group Z2 preferably includes one or two phenyl groups on which the group GR5 and the nitrogen atom continuing the polymer chain are bonded. The group GR5 and the nitrogen atom are preferably disposed in the ortho position relative to one another in order also to permit cyclization to give the oxazole in the case the groups Z2. The part-structures of the group Z2, in particular phenyl groups, which carry the groups GR5 can be linked via alkylene and/or arylene groups or via groups formed from hetero atoms. The groups Z2 can be substituted by monovalent groups, in particular alkyl groups. In particular, Z2 is a structural unit which is selected from the group:
in which R6 is a divalent substituent that is selected from the following group:
in which - R7 is an alkyl substituent having 1 to 10 carbon atoms or an aryl substituent having 5 to 22 carbon atoms; and
- e is an integer from 1 to 10.
- G in groups Z1 and Z2 is preferably an oxygen atom.
-
- The groups Y1 and Y2 may likewise have a very large variety of structures and preferably include 5 to 30 carbon atoms. The groups Y1 and Y2 may include saturated and unsaturated hydrocarbon groups as part-structures, aromatic hydrocarbon groups being preferred.
-
- f is an integer from 1 to 10; and
- g is an integer from 1 to 10.
- Poly-o-hydroxyamide of the Formula I may carry, as terminal groups E1 and E2, a hydrogen atom or a hydroxyl group or a saturated or unsaturated monovalent hydrocarbon substituent which may also contain one or more hetero atoms. The hydrocarbon substituent preferably includes 1 to 30 carbon atoms. Some examples of suitable terminal groups E1 and E2 are shown below.
-
-
- h is 0-10, and
- q is *—O—*, *—S—*, or *—NH—*.
- The terminal groups E1 and E2 can be introduced into the poly-o-hydroxyamides of the Formula I by corresponding active precursors, for example acid chlorides.
- The structures shown for the substituents Y1, Y2, E1, and E2 represent only a selection of preferred structures. However, this list should not be considered as being definitive.
- As already mentioned, the polybenzoxazoles obtained from the poly-o-hydroxyamides of the Formula I by cyclization have advantageous properties with respect to the thermal stability, the mechanical strength and the electrical insulating effect. The invention therefore also relates to polybenzoxazoles of the Formula III
in which
and a, b, c, d, R1, R2, R3, R4, R5, Y1, Y2, E1, E2, and G have the meaning stated in the case of Formula I. - For reasons of simplicity, both polybenzoxazoles (G=0) and polybenzothiazoles (G=S) of the Formula III are referred to as polybenzoxazoles. The structures of the groups shown in the Formula III are equally applicable to both classes of compounds. Formula III represents a polymer having a continuous polymer backbone. For reasons of simplicity, however, the molecule in Formula III has been shown in two parts.
- The poly-o-hydroxyamides of Formula I can be prepared by reacting bis-o-aminophenols or bis-o-aminothiophenols with dicarboxylic acids or their activated derivatives. The invention therefore also relates to monomers of the Formulae IVa and IVb:
in which R1, R2, R3, R4, R5, and G have the meanings stated in the case of Formula I. - The monomers of the Formulae IVa and IVb are prepared by customary synthesis processes, as described, for example, in Organikum, Wiley-VCH, 1999, page 228 et seq., page 324 et seq. and page 340 et seq. Similar monomers are described, for example, in U.S. Pat. No 4,525,539 or in European Patent No. EP 0 317 942.
- The monomers of the Formulae IVa and IVb can be reacted with dicarboxylic acids or their activated derivatives to give the desired poly-o-hydroxyamides of the Formula I. The invention therefore also relates to a process for the preparation of poly-o-hydroxyamides of the Formula I, monomers of the Formula IVa and/or IVb being reacted with a dicarboxylic acid or an activated dicarboxylic acid derivative of the Formulae Va and/or Vb.
in which L is a hydroxyl group or an activating group and Y1 and Y2 have the meaning stated in the case of Formula I. For example, acid chlorides or activated esters, for example sulfonic acid esters, can be used as an activating group for the dicarboxylic acid derivatives of the formula V. The reaction of the monomers of the Formula IVa or IVb and of the dicarboxylic acids of the Formulae Va and Vb can, however, also be effected in the presence of a compound that activates the carboxylic acid, such as, for example, carbonyldiimidazole or dicyclohexylcarbodiimide. In principle, all reagents which bind the water formed in the reaction to themselves are suitable. For the preparation of the poly-o-hydroxyamides of the Formula I, the monomers of the Formula IVa or IVb and the dicarboxylic acid(s) or optionally the dicarboxylic acid derivatives of the Formula Va or Vb are reacted in an organic solvent at −20 to 150° C. in the course of 5 to 20 hours. If required, terminal groups of the polymer can be blocked with a suitable reagent in order thus to introduce the terminal groups E1 and E2. Suitable-reagents have already been described in the explanation of the compounds of the Formula I. The poly-o-hydroxyamide of the formula I which has formed after the reaction is precipitated by dropwise addition of the reaction solution to a precipitating agent, washed and dried. Suitable precipitating agents are water and alcohols, such as isopropanol, butanol, or ethanol. Mixtures of these precipitating agents may also be used. It is also suitable for the precipitating agent to contain from 0.1% to 10% of ammonia. After filtration and drying, the precipitated polymer can be directly further processed and, for example for application to a semiconductor substrate, can be dissolved in one of the solvents mentioned further above. - The polymerization to give the poly-o-hydroxyamide of the Formula I can be carried out in the presence of a base in order to trap acid liberated. Suitable basic acid acceptors are, for example, pyridine, triethylamine, diazabicyclooctane, or polyvinylpyridine. However, other basic acid acceptors may also be used. Compounds that are readily soluble in the solvent used for the synthesis, for example N-methylpyrrolidone, and in the precipitating agent, for example water or water/alcohol mixtures, are those that are completely insoluble in the solvent, such as, for example, crosslinked polyvinylpyridine, are particularly preferred. The acid acceptors can then easily be separated from the resulting poly-o-hydroxyamide during the working up of the reaction product.
- Particularly suitable solvents for the polymer synthesis are γ-butyrolactone, tetrahydrofuran, N-methylpyrrolidone, and dimethylacetamide. However, any solvent in which the starting components are readily soluble can in principle be used.
- The invention furthermore relates to a process for the preparation of polybenzoxazoles of the Formula III, poly-o-hydroxyamides of the Formula I being heated. Heating results in the formation of an oxazole ring or thiazole ring with elimination of a small molecule, in general water, the polybenzoxazoles of the Formula III, according to the invention, being obtained. The pore formation that occurs is influenced only to a slight extent by the reaction conditions. The pores have a diameter in the region of a few ten nanometers and a narrow pore distribution. The process therefore permits large tolerances in the production of the dielectric, which substantially simplifies the reaction procedure.
- The polybenzoxazole of Formula III, which is prepared by the process according to the invention, has a very low dielectric constant of k≦2.5, owing to the pores enclosed in the dielectric. It adheres very well to surfaces relevant to chip technology, such as silicon, silicon carbide, silicon carbonitride, silicon nitride, silica, titanium, tantalum, titanium nitride, tantalum nitride, or silicon oxynitride. The invention therefore also relates to an electronic component that contains the polybenzoxazole of Formula III described above. Polybenzoxazole of Formula III may be disposed, for example, as a dielectric between conductor tracks or conductor track planes or as a buffer layer between the microchip and the housing surrounding it. The dielectrics according to the invention are outstandingly suitable for the copper damascene technique. During the grinding process, no disadvantageous effects, such as delamination, cracking or blister formation, occur.
- The invention therefore also relates to a process for the production of an electronic component, a solution of a poly-o-hydroxyamide of the Formula I in a solvent first being prepared. This solution is applied to a substrate and the solvent is evaporated so that a film is obtained. The film is then heated in order to cyclize the poly-o-hydroxyamide and convert it into the polybenzoxazole of Formula III. The film is then structured in order to obtain a resist structure which has trenches. A conductive material, for example copper, is then deposited on the resist structure so that the trenches are filled with a conductive material. Finally, excess conductive material is removed.
- For example, lithographic processes can be used for structuring the polybenzoxazole film, an etch-resistant mask being produced on the film. The structure of the mask is then transferred into the film of the polybenzoxazole according to the invention by etching. Copper is preferably used as conductive material. A barrier can be provided between dielectric and conductive material. For example, the materials already mentioned further above are suitable as material for the barrier. Excess conductive material is removed, for example, by chemical mechanical planarization.
- The invention furthermore relates to a process for the production of an electronic component, a solution of a poly-o-hydroxyamide of Formula I described above first being prepared in a solvent. The solution is then applied to a substrate that already has on its surface metallic structures between which trenches are formed. Such structures are, for example, conductor tracks. The solvent is evaporated so that the trenches are filled with the poly-o-hydroxyamide. Finally, the substrate is heated in order to cyclize the poly-o-hydroxyamide to give a polybenzoxazole.
- The adhesion of the polyhydroxyamides to surfaces relevant in microelectronics, such as, for example, silicon, silica, silicon nitride, tantalum nitride, glass or quartz, can be improved by adding adhesion promoters.
-
- Although the invention is illustrated and described herein as embodied in methods for producing a dielectric, a dielectric having self-generating pores, a monomer for porous dielectrics, a process for preparing poly-o-hydroxyamides, a process for preparing polybenzoxazoles, a processes for producing an electronic component, and a method for forming a dielectric, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
- The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
-
FIG. 1 is a partial diagrammatic and partial schematic drawing showing a setup according to the invention for determining an dielectric constant; and -
FIG. 2 is a photograph showing a shadow mask as used in example 25 for the production of electrodes. -
Stage 1 - The corresponding bishydroxybinaphthyl and 3-fluoro-6-nitrobenzyloxyphenol are initially introduced under inert gas (nitrogen or argon) into a three-necked flask that is provided with a stirrer and an inert gas connection, and N,N-dimethylformamide is added to these at room temperature. The mixture is stirred for about 10 to 20 minutes at room temperature. Thereafter, potassium carbonate is added in portions to the solution under inert gas. The solution is stirred at an elevated temperature for a few hours. The reaction temperature is suitably chosen from 60 to 140° C. The reaction occurs over course of 1 to 10 hours. In addition to N,N-dimethylformamide, for example, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, or dimethylacetamide can also be used. The concentrations of the starting materials are suitably chosen in a range from 5 to 50% by weight.
- The suspension formed is cooled to room temperature and poured into a cooled (2-10° C.), aqueous potassium hydroxide solution. The product is precipitated in crystalline form. The precipitation can be accelerated by adding ethyl acetate. The product is filtered, washed with water, and then added to a 10% strength solution of acetic acid in water. The solution is stirred for 15 to 30 minutes, filtered, washed with water and dried under inert gas at 40° C./100 mbar in a drying oven until the weight remains constant. The crude product obtained in this manner is recrystallized from a solution in tetrahydrofuran and petroleum ether and dried again under reduced pressure.
- Stage 2 (Hydrogenation and Simultaneous Elimination of the Benzyl Protective Group):
- The hydrogenation is effected by known hydrogenation processes for nitro compounds, as described, for example, in European Patent No. EP 905 121, example 8. For this purpose, the nitro compound obtained in
stage 1 can be dissolved, for example, in tetrahydrofuran, palladium on active carbon added and hydrogenation effected with hydrogen at superatmospheric pressure in an autoclave. - The bis((3-benzyloxy-4-nitro)phenoxy)binaphthyl prepared in
stage 1 is dissolved in tetrahdyrofuran, and palladium on active carbon is added under inert gas. The amount of Pd/C is about 10% of the amount of the compound to be hydrogenated. The suspension is introduced into a previously heated hydrogenation reactor under argon inert gas and hydrogenated with hydrogen at room temperature under pressure. The hydrogenation time is in general 10 to 50 hours. The hydrogen pressure is suitably chosen from 0.5 to 5 bar. The concentration of the compound to be hydrogenated in tetrahydrofuran is 5 to 30% by weight. Instead of tetrahydrofuran, for example, dioxane, halogenated hydrocarbons or toluene can also be used as the solvent. - After the hydrogenation, the suspension is transferred under inert gas into pure ethanol, and concentrated hydrochloric acid is added with stirring until a clear solution forms. After the product has completely dissolved, the solution is filtered over a Bütchner funnel in order to remove the Pd catalyst. Thereafter, about 70% of the amount of solvent is distilled off under reduced pressure and the concentrated solution is added to a solution of diethyl ether and acetone (volume ratio 7:3) with rapid stirring. During this procedure, the product is precipitated in crystalline form. The suspension is stored for 12-24 hours at 0° C. to 18° C. The product is then filtered off with suction and dried. The aminophenol is present as the hydrochloride. In contrast to the free aminophenol the form is not so greatly sensitive to oxidation by atmospheric oxygen.
-
Stage 1 - Moistened silica is initially introduced into a three-necked flask provided with a stirrer, a reflux condenser and an inert gas connection, and 10% strength sulfuric acid is added. The ratios are chosen at about 10 parts by weight of silica per 6 parts by weight of 10% strength sulfuric acid. 200 parts by weight of dichloromethane and 10 parts by weight of dihydroxybinaphthyl are then added in this sequence. About 10 parts by weight of 65% strength nitric acid are then added at a temperature of 2 to 10° C. in the course of 15 to 60 minutes. After the end of the addition, the suspension is stirred until quantitative conversion of the starting material at room temperature. The abovementioned ratio can be changed in a range of up to about 20%. Instead of dichloromethane, other halogenated hydrocarbons may also be used as the solvent.
- After complete conversion, the suspension is filtered. The product, which is present adsorbed onto the SiO2 surface, is dissolved in a suitable solvent, such as, for example, acetone or ethyl acetate, and filtered. This procedure is repeated twice. The organic fractions are combined and evaporated down. The concentrated solution is slowly poured into dimethyl ether while stirring, and the precipitated product is filtered off with suction. The product is then dried under inert gas at 40° C./100 mbar in a drying oven until the weight remains constant.
- Stage 2:
- The hydrogenation of the compound obtained in
stage 1 is carried out in the same manner as described in example 1. - Stage 1: 2,2′-Diacetoxy-3,3′-dinitro-1,1′-binaphthyl
- 4.088 g (14.29 mmol) of 2,2′-dihydroxy-1,1′-binaphthyl in 50 ml of acetic anhydride are initially introduced into a 250 ml three-necked flask provided with a reflux condenser, a KPG stirrer and an inert gas connection and are dissolved. A solution of 4.35 ml (42.80 mmol) of nitric acid (62%) in 25 ml of acetic anhydride is then added dropwise to the solution at 0° C. in the course of 30 min. At the same temperature, stirring is carried out for 4 h and the precipitated orange-red solid is filtered off with suction on a frit. After the end of the reaction, the mixture is carefully poured in 500 ml of ice water and thoroughly stirred. The solid nitro product is filtered off with suction and thoroughly washed with water.
- The crude product is dissolved in toluene at room temperature (2 ml/g) and heated to 90° C. and petroleum ether (4 ml/g) is added until crystallization begins. Thereafter, the suspension is slowly cooled to room temperature, and the suspension is stored for a further 4 h in a freezer at −18° C. and then filtered. The product obtained is dried for 24 h at 200 mbar and 55° C.
- Yield 5.72 g (87% of theory)
- Stage 2: 2,2′-Diacetoxy-3,3′-diamino-1,1′-binaphthyl hydrochloride
- The hydrogenation is effected according to known processes for the hydrogenation of nitro compounds, as described, for example, in European Patent No. EP 905 121, example 8.
- 31.09 g (67.57 mmol) of 2,2′-diacetoxy-3,3′-dinitro-1,1′-binaphthyl are dissolved in 600 ml of tetrahydrofuran, and 5.00 g of 5% Pd/C are added under inert gas. The suspension is introduced under Ar inert gas into a previously heated hydrogenation reactor and hydrogenated at room temperature for 24 h and under 2 bar H2 pressure.
- The suspension is then transferred under inert gas into 200 ml of ethanol. 10 ml of concentrated HCl are added with stirring and, when the product has completely dissolved, filtration is effected three times over a Büchner funnel to remove the Pd catalyst. The solution thus obtained is evaporated down to about 20 ml of ethanol at 70° C. and 300 mbar and then added to a solution of 700 ml of diethyl ether and 30 ml of acetone with rapid stirring. The suspension is stored for 24 h at −18° C. and the solid is filtered off and dried.
- Yield: 28.65 g (90% of theory)
- Preparation of the polymers
- Chemicals used
- Bisaminophenols:
-
-
-
-
-
- Dicarboxylic acid chlorides
-
-
-
-
-
-
- Endcaps (E1, E2):
-
-
-
- 50 g (0.1 mmol) of
bisaminophenol 1 are dissolved in 400 ml of distilled N-methylpyrrolidone (NMP). A solution of 23.93 g (0.095 mol) ofdicarboxylic acid chloride 1, dissolved in 200 ml of distilled NMP is added dropwise to this solution at 10° C. while stirring. Stirring is continued for a further hour at 10° C. and then for one hour at 20° C. After further cooling to 10° C., 1.64 g (0.01 mol) ofendcap 3, dissolved in 50 ml of distilled y-butyrolactone (γ-BL) are added dropwise to the reaction mixture, and stirring is carried out for one hour at 10° C. and then for one hour at 20° C. The reaction solution is cooled to 10° C., after which 19.76 g (0.25 mol) of pyridine, dissolved in 30 ml of distilled γ-BL, are added to said reaction solution and the latter is warmed up to room temperature and stirred for 2 hours. - In order to isolate the polymer, the reaction mixture is filtered and the filtrate is added dropwise to a mixture of 1 1 of demineralized water and 200 ml of isopropanol while stirring, a further 3 l of demineralized water being added during the dropwise addition. The precipitated polymer is filtered off with suction and washed with 2 l of cold demineralized water. After the filtration with suction, the polymer is stirred twice for 1 hour at room temperature in 2.5 portions of a 3% strength ammonia solution and then filtered off with suction. The polymer is washed neutral with demineralized water, filtered off, and dried for 72 hours at 50° C./10 mbar.
- The polymer prepared in this manner is readily soluble in solvents such as NMP, γ-BL, cyclohexanone, cyclopentanone or mixtures thereof.
- 15.81 g (0.05 mol) of
bisaminophenol 2 are dissolved in 200 ml of distilled NMP. A solution of 8.82 g (0.03 mol) ofdicarboxylic acid chloride 3 and 3.53 g (0.0175 mol) of dicarboxylic acid chloride 4 in 150 ml of distilled γ-BL is added dropwise to this solution at 10° C. while stirring. Stirring is continued for a further hour at 10° C. and then for 1 hour at 20° C. After further cooling to 10° C., 0.52 g (0.005 mol) ofendcap 1, dissolved in 20 ml of distilled γ-BL, is added dropwise to the reaction mixture, and stirring is carried out for 1 hour at 10° C. and then for 1 hour at 20° C. The reaction mixture is cooled to 10° C., after which 9.48 g (0.12 mol) of pyridine, dissolved in 30 ml of distilled γ-BL, are added to said reaction mixture and the latter is warmed up to room temperature and stirred for 2 hour. -
Polymer 2 is isolated and worked-up analogously to example 4. - 25 g (0.05 mol) of
bisaminophenol 1 are dissolved in 200 ml of distilled NMP. A solution of 5.56 g (0.02 mol) ofdicarboxylic acid chloride 2 in 80 ml of distilled γ-BL is added dropwise to this solution at 10° C. while stirring. Stirring is carried out for a further hour at 10° C. and then for 1 hour at 20° C. Cooling is effected at 10° C. and 5.55 g (0.0275 mol) of dicarboxylic acid chloride 4, dissolved in 80 ml of distilled γ-BL, are added dropwise. Stirring is carried out for a further hour at 10° C. and then for 1 hour at 20° C. After cooling to 10° C., 0.78 g (0.005 mol) ofendcap 2 dissolved in 20 ml of distilled γ-BL is added dropwise to the reaction mixture, and stirring is carried out for 1 hour at 10° C. and then for 1 hour at 20° C. The reaction mixture is cooled to 10° C., after which 11.85 g (0.15 mol) of pyridine, dissolved in 50 ml of distilled γ-BL, are added and said reaction mixture is warmed up to room temperature and stirred for 2 hours. -
Polymer 3 is isolated and worked-up analogously to example 4. - 25 g (0.05 mol) of
bisaminophenol 1 and 20 g (0.05 mol) ofbisaminophenol 5 are dissolved in 400 ml of distilled NMP. A solution of 27.93 g (0.095 mol) ofdicarboxylic acid chloride 3 in 150 ml of distilled γ-BL is added dropwise to this solution at 10° C. while stirring. Stirring is continued for a further hour at 10° C. and then for 1 hour at 20° C. After further cooling to 10° C., 1.64 g (0.01 mol) ofendcap 3, dissolved in 20 ml of distilled γ-BL, are added dropwise to the reaction mixture and stirring is carried out for 1 hour at 10° C. and then for 1 hour at 20° C. The reaction mixture is cooled to 10° C., after which 19.76 g (0.25 mol) of pyridine, dissolved in 50 ml of distilled γ-BL, are added and said reaction mixture is warmed up to room temperature and stirred for 2 hours. - Polymer 4 is isolated and worked-up analogously to example 4.
- 18.97 g (0.06 mol) of
bisaminophenol 2 and 15.2 g (0.04 mol) ofbisaminophenol 3 are dissolved in 300 ml of distilled NMP. A solution of 14.7 g (0.05 mol) ofdicarboxylic acid chloride 3 and 13.59 g (0.045 mol) ofdicarboxylic acid chloride 5, dissolved in 250 ml of distilled γ-BL, are added dropwise to this solution at 10° C. while stirring. Stirring is continued for 1 hour at 10° C. and for 1 hour at 200C. After further cooling to 10° C., 1.56 g (0.01 mol) ofendcap 2, dissolved in 50 ml of distilled γ-BL, are added dropwise to the reaction mixture, and stirring is carried out for 1 hour at 10° C. and then for 1 hour at 20° C. The reaction mixture is cooled to 10° C., after which 19.76 g (0.25 mol) of pyridine, dissolved in 50 ml of distilled γ-BL, are added and said reaction mixture is warmed up to room temperature and stirred for 2 hours. - The isolation and working-up of
polymer 5 are effected analogously to example 4. - 30.01 g (0.06 mol) of
bisaminophenol 1 are dissolved in 220 ml of distilled NMP. A solution of 11.11 g (0.055 mol) ofdicarboxylic acid chloride 1 in 80 ml of distilled γ-BL are added dropwise to this solution at 10° C. while stirring. Stirring is continued for 1 hour at 10° C. and for 1 hour at 20° C. Cooling is effected to 10° C. and 15.2 g (0.04 mol) ofbisaminophenol 3, dissolved in 80 ml of distilled γ-BL, are added dropwise. Stirring is continued for 1 hour at 10° C. and then for 1 hour at 20° C. Further cooling is effected to 10° C. and 12.08 g (0.04 mol) ofdicarboxylic acid chloride 5, dissolved in 80 ml of distilled 7-BL, are added dropwise. Stirring is carried out for a further hour at 10° C. and then for 1 hour at 20° C. After further cooling to 10° C., 1.04 g (0.01 mol) ofendcap 1, dissolved in 20 ml of distilled γ-BL, are added dropwise to the reaction mixture, and stirring is carried out for 1 hour at 10° C. and then for 1 hour at 20° C. The reaction mixture is cooled to 10° C., after which 19.76 g (0.25 mol) of pyridine, dissolved in 50 ml of distilled γ-BL, were added and said reaction mixture is warmed up to room temperature and stirred for 2 hours. -
Polymer 6 is isolated and worked-up analogously to example 4. - All polymers described have thermal stabilities of >480° C. according to TGA investigations (apparatus: STA 1500 from Rheometric Scientific, heating rate: 5 K/min, inert gas: argon). The isothermal mass loss per hour (at 425° C.) is <0.7%. The polymers described therefore meet the requirements for use as insulation in microchips.
- 25 g of the polymers described in examples 4 to 9 are dissolved in 75 g of distilled NMP or distilled γ-BL. The dissolution process is expediently effected on a shaking apparatus at room temperature. The solution is then filtered under pressure through a 0.2 μm filter into a cleaned, particle-free glass sample tube. The viscosity of the polymer solution can be changed by varying the dissolved mass of polymer.
- 0.5 g of adhesion promoter (e.g. N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane) are dissolved in 95 g of methanol, ethanol or isopropanol and 5 g of demineralized water at room temperature in a cleaned, particle-free sample tube. After standing for 24 h at room temperature, the adhesion promoter solution is ready for use. This solution is usable for 3 weeks at the most.
- The adhesion promoter should give a monomolecular layer on the surface of the parts to be adhesively bonded. The adhesion promoter can expediently be applied by the spin coating technique. For this purpose, the adhesion promoter solution is applied via a 0.2 μm prefilter to the surface to be adhesively bonded and is spun for 30 s at 5 000 rpm. A drying step is then effected for 60 s at 100° C.
- A processed silicon wafer that has lands and trenches up to a minimum dimension of, in each case, about 150 nm is coated, as described in example 10, with an adhesion promoter. The filtered solution of
polymer 1, which was obtained according to example 11, is then applied to the wafer by using a syringe and is uniformly distributed using a spin coater. The spin coater speed is 2,000 rpm. The polymer is then heated on a hotplate for 1 min at 120° C. and for 2 min at 200° C. The coated wafer is then heated under nitrogen or argon in an oven to 425° C. for 60 min. The polybenzoxazole thus obtained is inert to acids, bases and organic solvents. - A 4″ silicon wafer is sputtered with a 50 nm thick titanium nitride layer. The solution prepared in example 11 is applied to this wafer by spin coating, at 500 rpm for 5 s and at 2,000 rpm for 25 s. After a short softbake of 1 min at 120° C. on a hotplate, 10 silicon chips having an edge length of 4×4 mm2, which had likewise been sputtered with a 50 nm thick titanium nitride layer, are then pressed onto the polymer film with a force of 2 N. This stack is then heated in a nitrogen atmosphere for 1 h at 425° C. in an oven. Following cooling to room temperature, an adhesion test was carried out using a shear tester, Dage series 400. The mean value for
polymer 1 that was required for shearing off the chips is 15.51 N/mm2. - The experiment carried out was the same as that described in Example 14, but the surface of the wafer and of the chips was formed not of titanium nitride but of tantalum nitride. The mean value of the force for
polymer 1 that was required for shearing off the chips is 16.01 N/mm2. - The experiment carried out is the same as that described in Example 14, but the surface of the wafer and of the chips is formed not of titanium nitride but of silicon. The mean value of the force for
polymer 1 that was required for shearing off the chips is 17.05 N/mm2. - The experiment carried out is the same as that described in Example 14, but the surface of the wafer and of the chips is not formed of titanium nitride but of silicon nitride. The mean value of the force for
polymer 1 that was required for shearing off the chips is 15.16 N/mm2. - The experiment carried out is the same as that described in example 14, but the surface of the wafer and of the chips is formed not of titanium nitride but of silica. The mean value of the force for
polymer 1 that was required for shearing off the chips is 16.20 N/mm2. - The experiment carried out is the same as that described in Example 14, but the surface of the wafer and of the chips was not formed of titanium nitride but of silicon carbide. The mean value of the force for
polymer 1 that was required for shearing off the chips is 15.73 N/mm2. - The experiment carried out is the same as that described in Example 14, but the surface of the wafer and of the chips was not formed of titanium nitride but of tantalum. The mean value of the force for
polymer 1 that was required for shearing off the chips is 16.68 N/mm2. - The experiment carried out is the same as that described in example 14, but the surface of the wafer and of the chips were formed not of titanium nitride but of titanium. The mean value of the force for
polymer 1 that was required for shearing off the chips is 15.84 N/mm2. - The experiment carried out is the same as that described in Example 14, but the surface of the wafer and of the chips was not formed of titanium nitride but of polyimide. The mean value of the force for
polymer 1 that was required for shearing off the chips is 16.26 N/mm2. - A polymer was prepared analogously to Example 1 of U.S. Pat. No. 5,077,378 and a polymer solution in NMP was prepared as described in Example 11. The adhesion of the polymer was then determined as described in examples 14 to 22. The following mean values were found:
TABLE 1 Adhesion of the comparative polymers Surface Force for shearing off (N/mm2) Titanium nitride 14.71 Tantalum nitride 15.69 Silicon 15.21 Silicon nitride 14.03 Silica 14.94 Silicon carbide 13.37 Tantalum 13.96 Titanium 14.07 Polyimide 13.02 - The
polymer 1 was applied from a 20% strength solution (solvent: NMP) to a 4″ silicon wafer by spin coating, at 500 rpm for 5 s and at 2 000 rpm for 25 s. After a short softbake of 1 min at 120° C. and 2 min at 200° C. on a hotplate, the wafer is heated in a nitrogen atmosphere for 1 h at 400° C. in an oven. After cooling to room temperature, the coated wafer is heated in NMP to 80° C. for 5 h. Thereafter, the wafer is dried in vacuo for 60 min at 200° C. and the mass difference is determined. - The decrease in mass is 0.8%.
- The dielectric constant was measured using the configuration shown in
FIG. 1 . For this purpose, thepolymer 1 was dissolved in NMP (25% strength solution) and the solution was filtered under pressure through a membrane having 0.2 μM pores. This solution was applied by spin coating to asubstrate 1 on which a 600 nmthick titanium layer 2 is already present. Thelayer 3 is dried at 120° C. and 200° C., in each case for 2 min, on a hotplate and then heated at 430° C. for one hour in a nitrogen atmosphere. Titanium electrodes 4 are then sputtered onto thislayer 3 by using a shadow mask shown inFIG. 2 . For this purpose, the shadow mask shown inFIG. 2 includesorifices 5 which correspond to the position of the titanium electrodes 4. The dielectric constant is determined using theimpedance spectrometer 6 and is 2.31 in the frequency range from 100 Hz to 1 MHz. - The dielectric constant was determined analogously to example 25 in
polymers 2 to 5. The values found are shown in Table 2. - A polymer was prepared analogously to Example 1 of U.S. Pat. No. 5,077,378 and the dielectric constant is determined as described in example 25. The value found is likewise shown in Table 2.
TABLE 2 Dielectric constant of various polymers Example Polymer Dielectric constant 25 1 2.31 26 2 2.32 27 3 2.44 28 4 2.31 29 5 2.39 30 U.S. Pat. No. 5,077,378 Ex. 1 3.1
Claims (14)
1. A method for producing a dielectric, which comprises: using a poly-o-hydroxyamides of Formula I
where
E1 and E2, in each case independently, are substituents selected from the group consisting of hydrogen, a hydroxyl group, a saturated monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;
Y1 and Y2, in each case independently for each position, are a divalent hydrocarbon;
Z1, in each case independently for each position, is a structural unit having a formula selected from the group consisting of Formula IIa and IIb
the bond (-*) and the substituent -GR5 being disposed in the ortho position relative to one another,
Z2, in each case independently for each position, is a tetravalent hydrocarbon composed of groups linked to one another and selected from the group consisting of alkyl and aryl groups;
R1, R2, R3, and R4, in each case independently, are substituents selected from the group consisting of H, —C6H5, —(CH2)n—CH3, -G-(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)2, -G-CH(CH3)2, —C(CH3)3, -G-C(CH3)3, —(CF2)n—CF3, -G-(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —N(CH3)2, —N(CF3)2,
R5, in each case independently, is a substituent selected from the group consisting of H, —CO(CH2)n—CH3, —COO—(CH2)n—CH3, —(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)2, —C(CH3)3, —(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —(CH2)n—C6H5, —COO—(CH2)n—C6H5;
G is a heteroatom selected from the group consisting of oxygen and sulfur;
a is an integer from 0 to 1;
b has a value from 1 to 200;
c has a value from 0 to 200;
d is an integer from 0 to 1;
n is an integer from 0 to 5;
R6 is a divalent substituent selected from the group consisting of:
R7 is a substituent selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms and an aryl group having from 5 to 22 carbon atoms; and
e is an integer from 1 to 10.
2. The method according to claim 1 , wherein, in E1 and E2, the saturated monovalent hydrocarbon contains a heteroatom.
3. The method according to claim 1 , wherein, in E1 and E2, the unsaturated monovalent hydrocarbon contains a heteroatom.
4. The method according to claim 1 , wherein at least one of the Y1 substituents has a heteroatom.
5. The method according to claim 1 , wherein at least one of the Y2 substituents has a heteroatom.
6. The method according to claim 1 , wherein, in Z2, one of the groups has a heteroatom.
7. A monomer for the preparation of a poly-o-hydroxyamide usable in dielectrics, comprising a backbone having a formula selected from the group consisting of Formula IVa and IV
where
R1, R2, R3, and R4, in each case independently, are selected from the group of substituents selected from the group consisting of H, —C6H5, —(CH2)n—CH3, -G-(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)2, -G-CH(CH3)2, —C(CH3)3, -G-C(CH3)3, —(CF2)n—CF3, -G-(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —N(CH3)2, —N(CF3)2,
R5, in each case independently, is a substituent selected from the group consisting of H, —CO(CH2)n—CH3, —COO—(CH2)n—CH3, —(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)2, —C(CH3)3, —(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —(CH2)n—C6H5, —COO—(CH2)n—C6H5; and
G is a heteroatom selected from the group consisting of oxygen and sulfur.
8. A process for preparing poly-o-hydroxyamides, which comprises:
reacting the monomer according to claim 7 with a dicarboxylic acid having a formula selected from the group consisting of Formulae Va and Vb
where
L is a substituent selected from the group consisting of a hydroxyl group and an activating group; and
Y1 and Y2, in each case independently for each position, are a divalent hydrocarbon.
9. A process for preparing poly-o-hydroxyamides, which comprises:
reacting the monomer according to claim 7 with an activated dicarboxylic acid derivative having a formula selected from the group consisting of Formulae Va and Vb
where
L is a substituent selected from the group consisting of a hydroxyl group and an activating group; and
Y1 and Y2, in each case independently for each position, are a divalent hydrocarbon.
10. The process according to claim 8 , which further comprises carrying out the reacting step with a base.
11. The process according to claim 9 , which further comprises carrying out the reacting step with a base.
12. A process for preparing polybenzoxazoles having a Formula III
where
Z1 has a formula selected from the group consisting of
E1 and E2, in each case independently, are substituents selected from the group consisting of hydrogen, a hydroxyl group, a saturated monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;
Y1 and Y2, in each case independently for each position, are a divalent hydrocarbon;
Z2, in each case independently for each position, is a tetravalent hydrocarbon composed of groups linked to one another and selected from the group consisting of alkyl and aryl groups;
R1, R2, R3, and R4, in each case independently, are substituents selected from the group consisting of H, —C6H5, —(CH2)n—CH3, -G-(CH2)n—CH3, —CH((CH2)nCH3)2, —CH (CH3)2, -G-CH(CH3)2, —C(CH3)3, -G-C(CH3)3, —(CF2)n—CF3, -G-(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —N(CH3)2, —N(CF3)2,
R5, in each case independently, is a substituent selected from the group consisting of H, —CO(CH2)n—CH3, —COO—(CH2)n—CH3, —(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)2, —C(CH3)3, —(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —(CH2)n—C6H5, —COO—(CH2)n—C6H5;
G is a heteroatom selected from the group consisting of oxygen and sulfur;
a is an integer from 0 to 1;
b has a value from 1 to 200;
c has a value from 0 to 200; and
d is an integer from 0 to 1;
the method which comprises:
heating poly-o-hydroxyamides having a Formula I
where
E1 and E2, in each case independently, are substituents selected from the group consisting of hydrogen, a hydroxyl group, a saturated monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;
Y1 and Y2, in each case independently for each position, are a divalent hydrocarbon;
Z1, in each case independently for each position, is a structural unit having a formula selected from the group consisting of Formula IIa and IIb
in which the bond (-*) and the substituent -GR5 are disposed in the ortho position relative to one another,
Z2, in each case independently for each position, is a tetravalent hydrocarbon composed of groups linked to one another and selected from the group consisting of alkyl and aryl groups;
R1, R2, R3, and R4, in each case independently, are substituents selected from the group consisting of H, —C6H5, —(CH2)n—CH3, -G-(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)2, -G-CH(CH3)2, —C(CH3)3, -G-C(CH3)3, —(CF2)n—CF3, -G-(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —N(CH3)2, —N(CF3)2,
R5, in each case independently, is a substituent selected from the group consisting of H, —CO (CH2)n—CH3, —COO—(CH2)n—CH3, —(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)2, —C(CH3)3, —(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —(CH2)n—C6H5, —COO—(CH2)n—C6H5;
G is a heteroatom selected from the group consisting of oxygen and sulfur;
a is an integer from 0 to 1;
b has a value from 1 to 200;
c has a value from 0 to 200;
d is an integer from 0 to 1;
n is an integer from 0 to 5;
R6 is a divalent substituent selected from the group consisting of:
R7 is a substituent selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms and an aryl group having from 5 to 22 carbon atoms; and p1 e is an integer from 1 to 10.
13. A process for producing an electronic component, which comprises:
preparing a solution of a poly-o-hydroxyamide having a Formula I in a solvent
where
E1 and E2, in each case independently, are substituents selected from the group consisting of hydrogen, a hydroxyl group, a saturated monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;
Y1 and Y2, in each case independently for each position, are a divalent hydrocarbon;
Z1, in each case independently for each position, is a structural unit having a formula selected from the group consisting of Formula IIa and IIb
in which the bond (-*) and the substituent -GR5 are disposed in the ortho position relative to one another,
Z2, in each case independently for each position, is a tetravalent hydrocarbon composed of groups linked to one another and selected from the group consisting of alkyl and aryl groups;
R1, R2, R3, and R4, in each case independently, are substituents selected from the group consisting of H, —C6H5, —(CH2)n—CH3, -G-(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)2, -G-CH(CH3)2, —C(CH3)3, -G-C(CH3)3, —(CF2)n—CF3, -G-(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —N(CH3)2, —N(CF3)2,
R5, in each case independently, is a substituent selected from the group consisting of H, —CO(CH2)n—CH3, —COO—(CH2)n—CH3, —(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)2, —C(CH3)3, —(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —(CH2)n—C6H5, —COO—(CH2)n—C6H5;
G is a heteroatom selected from the group consisting of oxygen and sulfur;
a is an integer from 0 to 1;
b has a value from 1 to 200;
c has a value from 0 to 200;
d is an integer from 0 to 1;
n is an integer from 0 to 5;
R6 is a divalent substituent selected from the group consisting of:
R7 is a substituent selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms and an aryl group having from 5 to 22 carbon atoms; and
e is an integer from 1 to 10;
applying the solution to a substrate;
evaporating the solvent to obtain a film;
heating the film to cyclize the poly-o-hydroxyamide having the Formula I to yield a polybenzoxazole having a Formula III
where
Z1 has a formula selected from the group consisting of
E1 and E2, in each case independently, are substituents selected from the group consisting of hydrogen, a hydroxyl group, a saturated monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;
Y1 and Y2, in each case independently for each position, are a divalent hydrocarbon;
Z2, in each case independently for each position, is a tetravalent hydrocarbon composed of groups linked to one another and selected from the group consisting of alkyl and aryl groups;
R1, R2, R3, and R4, in each case independently, are substituents selected from the group consisting of H, —C6H5, —(CH2)n—CH3, -G-(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)2, -G-CH(CH3)2, —C(CH3)3, -G-C(CH3)3, —(CF2)n—CF3, -G-(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —N(CH3)2, —N(CF3)2,
R5, in each case independently, is a substituent selected from the group consisting of H, —CO (CH2)n—CH3, —COO—(CH2)n—CH3, —(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)2, —C(CH3)3, —(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —(CH2)n—C6H5, —COO—(CH2)n—C6H5;
G is a heteroatom selected from the group consisting of oxygen and sulfur;
a is an integer from 0 to 1;
b has a value from 1 to 200;
c has a value from 0 to 200; and
d is an integer from 0 to 1;
structuring the film to obtain a resist structure having trenches;
depositing a conductive material on the resist structure so that the trenches are filled with a conductive material; and
removing excess of the conductive material.
14. A process for producing an electronic component, which comprises:
preparing a solution of a poly-o-hydroxyamide in a solvent, the poly-o-hyroxyamide having a Formula I
where
E1 and E2, in each case independently, are substituents selected from the group consisting of hydrogen, a hydroxyl group, a saturated monovalent hydrocarbon, and an unsaturated monovalent hydrocarbon;
Y1 and Y2, in each case independently for each position, are a divalent hydrocarbon;
Z1, in each case independently for each position, is a structural unit having a formula selected from the group consisting of Formula IIa and IIb
in which the bond (-*) and the substituent -GR5 are disposed in the ortho position relative to one another,
Z2, in each case independently for each position, is a tetravalent hydrocarbon composed of groups linked to one another and selected from the group consisting of alkyl and aryl groups;
R1, R2, R3, and R4, in each case independently, are substituents selected from the group consisting of H, —C6H5, —(CH2)n—CH3, -G-(CH2)n—CH3, —CH((CH2)nCH3)2, —CH (CH3)2, -G-CH(CH3)2, —C(CH3)3, -G-C(CH3)3, —(CF2)n—CF3, -G-(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —N(CH3)2, —N(CF3)2,
R5, in each case independently, is a substituent selected from the group consisting of H, —CO(CH2)n—CH3, —COO—(CH2)n—CH3, —(CH2)n—CH3, —CH((CH2)nCH3)2, —CH(CH3)3)2, —C(CH3)3, —(CF2)n—CF3, —CF((CF2)nCF3)2, —CF(CF3)2, —C(CF3)3, —(CH2)n—C6H5, —COO—(CH2)n—C6H5;
G is a heteroatom selected from the group consisting of oxygen and sulfur;
a is an integer from 0 to 1;
b has a value from 1 to 200;
c has a value from 0 to 200;
d is an integer from 0 to 1;
n is an integer from 0 to 5;
R6 is a divalent substituent selected from the group consisting of:
R7 is a substituent selected from the group consisting of an alkyl group having from 1 to 10 carbon atoms and an aryl group having from 5 to 22 carbon atoms; and
e is an integer from 1 to 10;
applying the solution to a substrate having a surface with metallic structures and trenches formed between the metallic structures;
evaporating the solvent to fill the trenches with the poly-o-hydroxyamide of the Formula I; and
heating the substrate to cyclize the poly-o-hydroxyamide of the formula I to yield the polybenzoxazole having a Formula III.
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US11/439,455 US20060214139A1 (en) | 2002-04-26 | 2006-05-23 | Methods for producing a dielectric, dielectric having self-generating pores, monomer for porous dielectrics, process for preparing poly-o-hydroxyamides, process for preparing ploybenzoxazoles, and processes for producing an electronic component |
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DE10218788.6 | 2002-04-26 | ||
US10/424,376 US7108807B2 (en) | 2002-04-26 | 2003-04-28 | Methods for producing a dielectric, dielectric having self-generating pores, monomer for porous dielectrics, process for preparing poly-o-hydroxyamides, process for preparing polybenzoxazoles, and processes for producing an electronic component |
US11/439,455 US20060214139A1 (en) | 2002-04-26 | 2006-05-23 | Methods for producing a dielectric, dielectric having self-generating pores, monomer for porous dielectrics, process for preparing poly-o-hydroxyamides, process for preparing ploybenzoxazoles, and processes for producing an electronic component |
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DE (1) | DE10218788A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008049577A1 (en) * | 2006-10-25 | 2008-05-02 | Dsm Ip Assets B.V. | Organic opto-electronic devices |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4001279A (en) * | 1973-03-29 | 1977-01-04 | The Regents Of The University Of California | Asymmetric macrocycles containing oxygen and binaphthyl ring members |
US4525539A (en) * | 1982-12-02 | 1985-06-25 | E. I. Du Pont De Nemours And Company | Vulcanizable nitrile-containing perfluoroelastomer |
US5077378A (en) * | 1986-10-02 | 1991-12-31 | Hoechst Celanese Corporation | Polyamide containing the hexafluoroisopropylidene group |
US5776990A (en) * | 1991-09-13 | 1998-07-07 | International Business Machines Corporation | Foamed polymer for use as dielectric material |
US6531632B2 (en) * | 2000-03-10 | 2003-03-11 | Infineon Technologies Ag | Bis-o-aminophenols and o-aminophenolcarboxylic acids and process for preparing the same |
US20030060573A1 (en) * | 2001-07-26 | 2003-03-27 | Andreas Walter | Phenyl-linked oxazole cyanates as dielectrics having good adhesive and filling properties |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4845183A (en) | 1987-11-24 | 1989-07-04 | Hoechst Celanese Corporation | Heat resistant polyamide and polybenzoxazole from bis-((amino-hydroxyphenyl)hexafluoroisopropyl)diphenyl ethers |
-
2002
- 2002-04-26 DE DE10218788A patent/DE10218788A1/en not_active Withdrawn
-
2003
- 2003-04-28 US US10/424,376 patent/US7108807B2/en not_active Expired - Fee Related
-
2006
- 2006-05-23 US US11/439,455 patent/US20060214139A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4001279A (en) * | 1973-03-29 | 1977-01-04 | The Regents Of The University Of California | Asymmetric macrocycles containing oxygen and binaphthyl ring members |
US4525539A (en) * | 1982-12-02 | 1985-06-25 | E. I. Du Pont De Nemours And Company | Vulcanizable nitrile-containing perfluoroelastomer |
US5077378A (en) * | 1986-10-02 | 1991-12-31 | Hoechst Celanese Corporation | Polyamide containing the hexafluoroisopropylidene group |
US5776990A (en) * | 1991-09-13 | 1998-07-07 | International Business Machines Corporation | Foamed polymer for use as dielectric material |
US6531632B2 (en) * | 2000-03-10 | 2003-03-11 | Infineon Technologies Ag | Bis-o-aminophenols and o-aminophenolcarboxylic acids and process for preparing the same |
US20030060573A1 (en) * | 2001-07-26 | 2003-03-27 | Andreas Walter | Phenyl-linked oxazole cyanates as dielectrics having good adhesive and filling properties |
Also Published As
Publication number | Publication date |
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US7108807B2 (en) | 2006-09-19 |
US20040028821A1 (en) | 2004-02-12 |
DE10218788A1 (en) | 2003-11-20 |
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