CN116508131A - 制造硅质含氮膜的方法 - Google Patents
制造硅质含氮膜的方法 Download PDFInfo
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- CN116508131A CN116508131A CN202180078241.6A CN202180078241A CN116508131A CN 116508131 A CN116508131 A CN 116508131A CN 202180078241 A CN202180078241 A CN 202180078241A CN 116508131 A CN116508131 A CN 116508131A
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- Prior art keywords
- film
- containing film
- nitrogen
- electron beam
- polysilazane
- Prior art date
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000010894 electron beam technology Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 32
- 229920001709 polysilazane Polymers 0.000 claims abstract description 32
- 239000012298 atmosphere Substances 0.000 claims abstract description 30
- 230000001590 oxidative effect Effects 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 230000001678 irradiating effect Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000005227 gel permeation chromatography Methods 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 abstract description 19
- 239000001301 oxygen Substances 0.000 abstract description 19
- 238000009832 plasma treatment Methods 0.000 abstract description 7
- 230000005855 radiation Effects 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- -1 hydroxy, amino, carbonyl Chemical group 0.000 description 19
- 229910052710 silicon Inorganic materials 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 229910052581 Si3N4 Inorganic materials 0.000 description 9
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- 230000001133 acceleration Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- LGCMKPRGGJRYGM-UHFFFAOYSA-N Osalmid Chemical compound C1=CC(O)=CC=C1NC(=O)C1=CC=CC=C1O LGCMKPRGGJRYGM-UHFFFAOYSA-N 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Chemical class CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical class CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical class C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910007991 Si-N Inorganic materials 0.000 description 2
- 229910006294 Si—N Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical class C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical class CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical class CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isononane Chemical class CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical class CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical class CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical class CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical class CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical class CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- IHJUECRFYCQBMW-UHFFFAOYSA-N 2,5-dimethylhex-3-yne-2,5-diol Chemical compound CC(C)(O)C#CC(C)(C)O IHJUECRFYCQBMW-UHFFFAOYSA-N 0.000 description 1
- ZWNMRZQYWRLGMM-UHFFFAOYSA-N 2,5-dimethylhexane-2,5-diol Chemical compound CC(C)(O)CCC(C)(C)O ZWNMRZQYWRLGMM-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- NUYADIDKTLPDGG-UHFFFAOYSA-N 3,6-dimethyloct-4-yne-3,6-diol Chemical compound CCC(C)(O)C#CC(C)(O)CC NUYADIDKTLPDGG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical class CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000001602 bicycloalkyls Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Chemical class CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000004404 heteroalkyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Chemical class CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229930004008 p-menthane Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Chemical class 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Chemical class C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- 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
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02345—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light
- H01L21/02351—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light treatment by exposure to corpuscular radiation, e.g. exposure to electrons, alpha-particles, protons or ions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—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
- H01L21/02123—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
- H01L21/0217—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 being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—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
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Abstract
公开了一种制备硅质含氮膜的方法。聚硅氮烷膜暴露于电子束辐射,随后暴露于从真空紫外光辐射和等离子体处理中选出的至少一种工艺。处理过的膜在非氧化气氛中加热以制造硅质含氮膜。硅质含氮膜能够在低工艺温度下形成。此外,硅质含氮膜具有高折射率和低的氧含量。
Description
技术领域
本发明涉及无机膜的制造,特别是应用于硅质含氮膜(silicon nitrogeneousfilm)的制造。此外,本发明还涉及包含该硅质含氮膜的半导体器件等的制造方法。
背景技术
在电子器件特别是半导体器件的制造中,化学惰性介电材料例如氮化硅是必不可少的。氮化硅薄膜用作扩散掩模、蚀刻工艺的硬掩模、氧化屏障、沟槽隔离、具有高介电击穿电压的层间介电材料。可以在晶体管元件与位线之间、位线与电容器之间、电容器与金属布线之间、多个金属布线之间等形成层间绝缘膜。此外,根据抑制布线迁移、抑制硅晶圆损坏、先进器件所用材料的热阻率等要求,需要降低制膜工艺的温度。
化学气相沉积法(CVD法)、溶胶-凝胶法、施涂含有含硅聚合物的组合物并烘烤的方法等用于形成氮化硅膜的方法。其中,使用组合物形成氮化硅膜的方法比较简单。
一直需要一种材料能够填充半导体器件的窄且具有高的深宽比的沟槽,并且可以通过在低工艺温度下固化转化为氮化硅膜,其耐酸蚀刻并且具有高折射率。
US 2009/289284 A1公开了一种制备氮化硅膜的方法,包括将全氢聚硅氮烷旋涂到基材上,在100至200℃的温度下烘烤全氢聚硅氮烷膜,并在氮气环境中,在200至500℃的温度下将烘烤过的全氢聚硅氮烷膜固化。
JP 1995206410 A公开了一种氮化硅膜的形成方法,其特征在于将全氢聚硅氮烷溶液施涂在基材上,并在低于500℃的温度下烘烤全氢聚硅氮烷膜,同时用紫外光照射。
JP 4049841 B公开了一种氮化硅膜的形成方法,包括将通过全氢聚硅氮烷溶解在有机溶剂中制备的全氢聚硅氮烷溶液施涂在基材上形成涂膜,干燥该涂膜并在高于600℃的温度下在真空中烘烤经干燥的涂膜。
US 5,093,096公开了一种生产氮化硅纤维的方法,包括将聚硅氮烷的纺丝溶液纺丝,在真空或非氧化性气氛中用剂量为5×107至9×109rad的电离辐射束照射该纤维并在温度为600至1700℃的氨气流中烧制经照射的纤维。
US 6,426,127 B1公开了一种在基材上形成介电涂层的方法,包括将含硅氮烷聚合物的组合物施涂到基材上,视情况加热该组合物以从其蒸发任何溶剂,并在足以固化该含硅氮烷聚合物的组合物的条件下用电子束辐射全面照射该组合物。电子束剂量落入约1至约500,000μC/cm2的范围内。
相关技术文献
专利文献1:US 2009/289284 A1
专利文献2:JP 1995206410 A
专利文献3:JP 4049841 B
专利文献4:US 5,093,096
专利文献5:US 6,426,127 B1
发明内容
本发明的一种实施方案提供了一种制造硅质含氮膜的方法,包括:
将包含聚硅氮烷和溶剂的硅质含氮膜成膜组合物施涂在基材上方以形成涂膜,
在非氧化气氛中对涂膜照射电子束,
进行至少一种从由以下构成的群组中选出的工艺:(a)在非氧化气氛中对电子束照射过的涂膜照射真空紫外光;和(b)对电子束照射过的涂膜进行等离子体处理,以及
在非氧化气氛中加热上一步骤处理过的涂膜。
本发明的另一种实施方案提供了一种能形成在窄且具有高的深宽比的沟槽中的硅质含氮膜。
本发明的又一实施方案提供了一种制造具有耐酸蚀的硅质含氮膜的电子器件的方法。
本发明的制造硅质含氮膜的方法能够以简单的工艺和低的工艺温度获得硅质含氮膜。能够在窄且具有高的深宽比的沟槽中形成硅质含氮膜。此外,硅质含氮膜能够耐受在半导体器件等的制造工艺中的酸蚀刻。硅质含氮膜还具有高折射率和低的氧含量。使用制造硅质含氮膜的方法可以提高电子器件的成品率。
定义
除非另有说明,否则在说明书和权利要求书中使用的以下术语对于本说明书的目的应具有以下含义。
在本说明书中,除非另有特别说明,否则单数的使用包括复数,并且词语“一”、“一个”和“该”意味着“至少一个”。此外,术语“包括”的使用以及诸如“包含”和“含有”的其他形式的使用不是限制性的。此外,除非另有具体说明,否则诸如“元件”或“组件”的术语涵盖:包含一个单元的元件或组件,以及包含多于一个单元的元件或组件。如本文所用,除非另有说明,否则连词“和”旨在是包括性的,而连词“或”并非旨在是排他性的。例如,短语“或者,替代地”旨在是排他的。如本文所用,术语“和/或”是指要素的任何组合,包括使用单一要素。
术语“约”或“大约”,当与可测定的数值变量结合使用时,是指变量的指示值以及在指示值的实验误差内(例如,平均值的95%置信限度内)或指示值的±10%以内的变量的所有值,以较大者为准。
在本说明书中,诸如“Cx-y”、“Cx-Cy”和“Cx”的描述是指分子或取代基中的碳原子数。例如,C1-6烷基是指具有不少于1且不多于6个碳的烷基(甲基、乙基、丙基、丁基、戊基、己基等)。
在本说明书中,除非另有说明,否则“烷基”是指直链或支链的烷基,“环烷基”是指含有环状结构的烷基。其中环状结构上取代有直链或支链烷基的那些也称为环烷基。此外,具有多环结构如双环烷基的那些也包括在环烷基中。“杂烷基”是指在主链或侧链中含有氧或氮的烷基,除非另有特别说明,例如是指包括氧基、羟基、氨基、羰基等在内的烷基。此外,“烃基”是指包含碳和氢并且视情况包含氧或氮的一价、二价或更高价的基团。此外,在本说明书中,除非另有特别说明,否则“亚烷基”是指对应于所述烷基的二价基团并且包括例如直链亚烷基或具有侧链的支链亚烷基。
在本说明书中,“含氮硅质”是指包含硅-氮键的无定形化学化合物,其可以含有氢、氧或碳。
在数值范围用“至”、“-”或“~”描述的情况下,这些包括端点并且单位是通用的。例如,5~25mol%是指5mol%以上且25mol%以下。
在本说明书中,“非氧化气氛”是指氧浓度为1ppm以下且露点为-76℃以下的气氛。
在本说明书中,在聚合物包含多种重复单元而没有任何具体定义的情况下,这些重复单元共聚。这些共聚可以采取交替共聚、无规共聚、嵌段共聚、接枝共聚或它们的任意混合形式。
在本说明书中,除非另有特别说明,均采用摄氏温度作为温度单位。例如,20度表示20摄氏度。
在本说明书中,除非另有特别说明,“%”表示“质量%”,“份”表示“质量份”。
本文中使用的章节标题是出于组织目的,不应被解释为限制所描述的主题。本申请中引用的所有文件或文件的部分,包括但不限于专利、专利申请、文章、书籍和论文,在此通过引用明确地全文并入于此用于任何目的。如果所并入的文献和类似材料中的一篇或多篇以与本申请中术语的定义相矛盾的方式定义该术语,则以本申请为准。
具体实施方式
下面详细描述本发明的实施方案。
制造含氮硅质膜的方法
根据本发明的制造硅质含氮膜的方法包括:
将包含聚硅氮烷和溶剂的硅质含氮膜成膜组合物施涂在基材上方以形成涂膜,
在非氧化气氛中对涂膜照射电子束,
进行至少一种从由以下构成的群组中选出的工艺:(a)在非氧化气氛中对电子束照射过的涂膜照射真空紫外光;和(b)对电子束照射过的涂膜进行等离子体处理,以及
在非氧化气氛中中加热上一步骤处理过的涂膜。
硅质含氮膜成膜组合物
本发明的硅质含氮膜成膜组合物包含聚硅氮烷和溶剂。
在不损害本发明的效果的范围内,本发明的制造方法中使用的聚硅氮烷可以自由选择。这些是无机化合物或有机化合物,并且可以是直链的、支链的或者部分具有环状结构。
优选地,该聚硅氮烷包含由下式(1)表示的重复单元:
其中R1至R3各自独立地为单键、氢或C1-4烷基。
更优选地,根据本发明的制备方法中使用的聚硅氮烷是全氢聚硅氮烷(以下简称“PHPS”)。PHPS是一种含硅聚合物,包含Si-N键作为重复单元,仅由Si、N和H组成。在这种PHPS中,除Si-N键外,所有与Si和N键合的元素都是H,基本上不含其他元素例如碳或氧。
PHPS在分子中具有支链结构或环状结构,并且这种PHPS的具体部分结构的例子如下式所示。
从在溶剂中的溶解性和反应性的观点来看,在根据本发明的制造方法中使用的聚硅氮烷的质均分子量优选为900至15,000,并且更优选为900至10,000。质均分子量是聚苯乙烯换算的质均分子量,并且可以通过以聚苯乙烯为基准的凝胶渗透色谱法测定。
可以使用多种溶剂来制备组合物。合适的溶剂包括但不限于芳族化合物,例如苯、甲苯、二甲苯、乙苯、二乙苯、三甲苯和三乙苯;饱和烃化合物,例如环己烷、十氢萘、双戊烯(dipentene)、正戊烷、异戊烷、正己烷、异己烷、正庚烷、异庚烷、正辛烷、异辛烷、正壬烷、异壬烷、正癸烷、乙基环己烷、甲基环己烷、环己烷和对薄荷烷;不饱和烃化合物,例如环己烯;醚类化合物,例如二丙醚、二丁醚和苯甲醚;酯类化合物,例如乙酸正丁酯、乙酸异丁酯、乙酸正戊酯和乙酸异戊酯;酮类化合物,例如甲基异丁基酮(MIBK)。溶剂可以单独使用或者两种或更多种组合使用。通过使用多种溶剂,可以调整聚硅氮烷的溶解度和溶剂的蒸发速率。
考虑到所采用的涂布方法的可加工性和组合物进入微细沟槽的渗透性以及沟槽外所需的膜厚度,可以根据所使用的聚硅氮烷的质均分子量适当地选择组合物中溶剂的量。基于组合物的总质量,本发明的组合物通常含有1至50质量%,优选1至30质量%的聚硅氮烷。
根据本发明的制造方法中使用的组合物可以包含可选(视情况使用的)组分,例如表面活性剂等。表面活性剂可以提高涂布性,因此是优选使用的。可用于本发明组合物的表面活性剂的例子包括非离子表面活性剂、阴离子表面活性剂、两性表面活性剂等。
非离子表面活性剂的例子包括聚氧乙烯烷基醚,例如聚氧乙烯月桂基醚、聚氧乙烯油基醚和聚氧乙烯鲸蜡基醚;聚氧乙烯脂肪酸二酯;聚氧脂肪酸单酯;聚氧乙烯聚氧丙烯嵌段聚合物;炔属醇;炔二醇;炔属醇衍生物,例如炔属醇的聚乙氧基化物;炔二醇衍生物,例如炔二醇的聚乙氧基化物;含氟表面活性剂,例如Fluorad(商品名,由3M Japan Limited制造)、Megafac(商品名,由DIC Corporation制造)、Surufuron(商品名,由Asahi GlassCo.,Ltd.制造)等;或者有机硅氧烷表面活性剂,例如KP341(商品名,由Shin-EtsuChemical Co.,Ltd.制造)。所述炔二醇的例子包括3-甲基-1-丁炔-3-醇、3-甲基-1-戊炔-3-醇、3,6-二甲基-4-辛炔-3,6-二醇、2,4,7,9-四甲基-5-癸炔-4,7-二醇、3,5-二甲基-1-己炔-3-醇、2,5-二甲基-3-己炔-2,5-二醇、2,5-二甲基-2,5-己二醇等。
阴离子表面活性剂的例子包括烷基二苯醚二磺酸的铵盐或有机胺盐、烷基二苯醚磺酸的铵盐或有机胺盐、烷基苯磺酸的铵盐或有机胺盐、铵盐或聚氧乙烯烷基醚硫酸的有机胺盐、烷基硫酸的铵盐或有机胺盐等。
两性表面活性剂的例子包括2-烷基-N-羧甲基-N-羟乙基咪唑鎓甜菜碱、月桂酰胺丙基羟砜甜菜碱等。
这些表面活性剂可以单独使用或作为两种或更多种的混合物使用,并且基于组合物的总质量,它们的混合比通常为50至10,000ppm,优选100至5,000ppm。
施涂硅质含氮膜成膜组合物
将硅质含氮膜成膜组合物施涂到此类基材上的方法没有特别限制并且包括通常的涂布方法,例如旋涂、浸涂、喷涂、转印法、辊涂、棒涂、涂布、刮涂、刷涂、流涂或狭缝涂布等。其上施涂组合物的合适基材是例如硅基材、玻璃基材和树脂膜。可以根据需要在这些基材上形成半导体器件等。
在施涂硅质含氮膜成膜组合物之后,为了使涂膜干燥,优选进行预烘烤步骤。预烘烤步骤在空气中或优选在非氧化气氛中进行。处理条件例如是在50至200℃下在热板上进行10秒至30分钟。
照射电子束
由硅质含氮膜成膜组合物形成的涂膜暴露于电子束。电子束由0.1至10mA,优选0.1至8mA的管电流产生。加速电压为50至100kV,优选为50至80kV。当加速电压低于50kV时,根据膜厚度,在涂膜底部周围向硅质含氮膜的转化不充分。当加速电压超过100kV时,半导体器件可能会受到影响。
电子束的照射剂量为10至100MGy,优选10至80MGy。
电子束照射在20至100℃下在非氧化气氛中进行。非氧化性气氛是指氧浓度为1ppm以下且露点为-76℃以下的气氛。优选地,使用N2、Ar、He、Ne、H2或这些中任何两种或更多种的混合物的气氛。
电子束照射过的膜的后处理
(a)将电子束照射过的膜暴露于真空紫外光。优选使用波长为100至200nm的真空紫外光作为本发明的真空紫外光辐射。产生真空紫外光的装置的例子包括:低压汞灯、准分子灯(单一波长126nm(Ar)、146nm(Kr)、165nm(ArBr)、172nm(Xe)和193nm(ArF))。其中,在本发明中优选使用发出172nm波长的Xe准分子灯。
所述真空紫外光的照度范围为1至200mW/cm2,优选10至100mW/cm2。真空紫外光剂量在3至15J/cm2范围内,优选在5至12J/cm2范围内。
真空紫外光照射在10至100℃下非氧化气氛中进行。优选地,使用N2、Ar、He、Ne、H2或这些中任何两种或更多种的混合物的气氛。
电子束照射和真空紫外光照射通过使用配备有真空紫外光(172nm)照射设备(M.D.COM Inc.)的EB-ENGIN L12978(Hamamatsu Photonics K.K.)进行。
(b)对电子束照射过的膜进行等离子体处理。等离子体由引入到等离子体处理室中的气体产生。气体的例子包括但不限于N2、H2、He、Ar、Ne、Xe、含碳气体、含氯气体以及它们的任何混合物。在这些气体中,优选N2或Ar。在优选50至300℃、更优选80至250℃的基材温度下进行等离子体处理,优选进行10至60分钟,更优选15至45分钟。腔室内的压力优选为0.1Pa至0.4MPa,更优选为1Pa至0.3MPa。气体供应流速优选为5,000至50,000标准cc/分钟(sccm),更优选为10,000至30,000sccm。
对处理过的涂膜加热
在非氧化气氛中对处理过的涂膜加热。优选地,使用N2、Ar、He、Ne、H2或这些中任何两种或更多种的混合物的气氛。加热可在300至800℃的温度范围内进行。在低于300℃的温度下加热会影响本发明的硅质含氮膜的膜性能。加热在VF-1000炉(Koyo ThermoSystemsCo.,Ltd.)中进行。
至目标温度的加热速率和加热过程中的冷却速率没有特别限制并且通常可以在从1℃至100℃/分钟的范围内。另外,达到目标温度后的保持时间也没有特别限定,通常可以在1分钟至10小时的范围内。
本发明的硅质含氮膜的膜厚没有特别限制,但优选为0.1至1.2μm,更优选为0.1至1.0μm。
本发明的硅质含氮膜的折射率为1.75至2.00,优选1.80至2.00,通过光谱椭偏仪(M-2000V JA Woollam Co.,Inc.)测量。硅、氮和氧含量通过X射线光电子能谱仪(PHIQuanteraII ULVAC PHI,Inc.)测量。基于硅、氮和氧的总质量,硅质含氮膜的氧含量为0.5至7质量%,优选0.5至6质量%。
本发明的电子器件的制造方法包括上述方法。优选地,该器件是半导体器件、太阳能电池芯片、有机发光二极管和无机发光二极管。本发明器件的优选实施方案之一是半导体器件。
实施例
在下文中,将通过发明实施例来描述本发明。这些实施例仅出于说明目的而给出,并不旨在限制本发明的范围。
合成例1
将配备有冷却冷凝器、机械搅拌器和温度控制器的10L反应容器内部用干燥氮气置换,然后将7,500mL干燥吡啶放入到反应容器中,然后冷却至-3℃。然后,加入500g二氯硅烷生成白色固体加合物(SiH2Cl2·2C5H5N)。确认反应混合物变为-3℃或更低后,在搅拌的同时将350g氨缓慢吹入到反应混合物中。随后,继续搅拌30分钟,然后将干燥的氮气吹入到液层中30分钟以除去过量的氨。在干燥氮气氛中,使用0.2μm的Teflon(注册商标)过滤器对所得浆状物进行加压过滤,得到滤液6000ml。用蒸发器蒸出吡啶,得到浓度为38.9%的无机聚硅氮烷的二甲苯溶液。
将配备有冷却冷凝器、机械搅拌器和温度控制器的10L反应容器内部用干燥氮气置换,然后加入4680g干燥吡啶、151g干燥二甲苯和1673g的38.9%的反应产物。在以0.5NL/min鼓入氮气的同时将它们搅拌均匀。随后,在100℃下进行重整反应13小时以获得重均分子量为4266的全氢聚硅氮烷。
合成例2
将配备有冷却冷凝器、机械搅拌器和温度控制器的10L反应容器内部用干燥氮气置换,然后将7,500mL干燥吡啶放入到反应容器中,然后冷却至-3℃。加入500g二氯硅烷生成白色固体加合物(SiH2Cl2·2C5H5N)。确认反应混合物变为-3℃或更低后,将混合物溶液搅拌1小时并将470g甲胺吹入到溶液中并在-3℃的反应温度下进行氨解100分钟。接着,在搅拌的同时将80g氨缓慢吹入到反应混合物中,将温度保持在-3℃并搅拌30分钟后,将干燥的氮气吹入到液层中30分钟除去过量的氨。在干燥氮气氛中,使用0.2μm的Teflon(注册商标)过滤器对所得浆状物进行加压过滤,得到滤液6000ml。用蒸发器蒸出吡啶,得到重均分子量(Mw)为1700、浓度为30.0%的N-甲基聚硅氮烷的二甲苯溶液。通过对所得树脂进行FT-IR光谱测定,确认生成了含有甲胺骨架的聚硅氮烷化合物,树脂的NH/SiH比为0.10。根据1HNMR谱图,NMe/SiH1,2比率为0.21,SiH3/SiH1,2比率为0.11。
实施例1
将合成例1的全氢聚硅氮烷溶液用二甲苯稀释成7.5质量%的溶液,使用1HDX2(Mikasa Co.Ltd.)旋涂在硅晶圆上。将涂膜在氮气氛中在热板上以80℃预烘烤3分钟。通过使用配备有真空紫外光(172nm)照射设备(M.D.COM Inc.)的EB-ENGIN L12978(HamamatsuPhotonics K.K.)将预烘烤过的膜暴露于电子束。电子束照射在25℃下在N2气氛中进行。电子束由7.5mA的管电流产生。加速电压为70kV,电子束的照射剂量为60MGy。
通过使用配备有真空紫外光(172nm)照射设备(M.D.COM Inc.)的EB-ENGINL12978(Hamamatsu Photonics K.K.)将电子束照射过的膜暴露于波长为172nm的真空紫外光。真空紫外光的照度为25mW/cm2,真空紫外光的剂量为9J/cm2。真空紫外光照射在N2气氛中在25℃下进行。
将真空紫外光照射过的膜在非氧化气氛中在450℃下加热90分钟。硅质含氮膜的折射率为1.82,膜厚为0.28μm。硅质含氮膜的氧含量为4.6质量%。
准备表面具有宽度为20nm、深度为500nm的沟槽结构的硅基材。通过上述方法制备硅质含氮膜。垂直于沟槽方向切割具有硅质含氮膜的硅基材。将硅基材条浸入到0.5%的氢氟酸水溶液中30秒。通过扫描电子显微镜观察截面。沟槽的底部耐受0.5%的氢氟酸水溶液。
实施例2
将合成例2的N-甲基聚硅氮烷溶液用二甲苯稀释成9.0质量%的溶液,使用1HDX2(Mikasa Co.Ltd.)旋涂在硅晶圆上。将涂膜在氮气氛中在热板上以80℃预烘烤3分钟。通过使用配备有真空紫外光(172nm)照射设备(M.D.COM Inc.)的EB-ENGIN L12978(HamamatsuPhotonics K.K.)将预烘烤过的膜暴露于电子束。电子束照射在25℃下在N2气氛中进行。电子束由7.5mA的管电流产生。加速电压为70kV,电子束的照射剂量为15MGy。
通过使用配备有真空紫外光(172nm)照射设备(M.D.COM Inc.)的EB-ENGINL12978(Hamamatsu Photonics K.K.)将电子束照射过的膜暴露于波长为172nm的真空紫外光。真空紫外光的照度为25mW/cm2,真空紫外光的剂量为10J/cm2。真空紫外光照射在N2气氛中在25℃下进行。
将真空紫外光照射过的膜在非氧化气氛中在600℃下加热90分钟。硅质含氮膜的折射率为1.88,膜厚为0.31μm。硅质含氮膜的氧含量为3.0质量%。
实施例3
将合成例1的全氢聚硅氮烷溶液用二甲苯稀释成10.0质量%的溶液,并使用1HDX2(Mikasa Co.Ltd.)旋涂在硅晶圆上。将涂膜在氮气氛中在热板上以80℃预烘烤3分钟。通过使用配备有真空紫外光(172nm)照射设备(M.D.COM Inc.)的EB-ENGIN L12978(HamamatsuPhotonics K.K.)将预烘烤过的膜暴露于电子束。电子束照射在25℃下在N2气氛中进行。电子束由7.5mA的管电流产生。加速电压为70kV,电子束的照射剂量为96MGy。
通过使用配备有真空紫外光(172nm)照射设备(M.D.COM Inc.)的EB-ENGINL12978(Hamamatsu Photonics K.K.)将电子束照射过的膜暴露于波长为172nm的真空紫外光。真空紫外光的照度为25mW/cm2,真空紫外光剂量为7J/cm2。真空紫外光照射在N2气氛中在25℃下进行。
将真空紫外光照射过的膜在非氧化气氛中在800℃下加热90分钟。硅质含氮膜的折射率为1.95,膜厚为0.25μm。硅质含氮膜的氧含量为0.8质量%。
实施例4
对实施例1的电子束照射过的膜进行等离子体处理。将电子束照射过的膜放置在大气压等离子体表面处理装置AP-TO2(Sekisui Chemical Co.,Ltd.)中。直接等离子体处理在200℃下进行30分钟。腔室内压力为0.1MPa,电极间电压为15kV。气体供应流速为20,000sccm的96vol%的N2和4vol%的H2。
将等离子体处理过的膜在非氧化气氛中在450℃下加热90分钟。硅质含氮膜的折射率为1.79,膜厚为0.25μm。硅质含氮膜的氧含量为4.9质量%。
对比例1
将合成例1的全氢聚硅氮烷溶液用二甲苯稀释成7.5质量%的溶液,使用1HDX2(Mikasa Co.Ltd.)旋涂在硅晶圆上。将涂膜在氮气氛中在热板上以80℃预烘烤3分钟。通过使用配备有真空紫外光(172nm)照射设备(M.D.COM Inc.)的EB-ENGIN L12978(HamamatsuPhotonics K.K.)将预烘烤过的膜暴露于电子束。电子束照射在25℃下在N2气氛中进行。电子束由7.5mA的管电流产生。加速电压为70kV,电子束的照射剂量为60MGy。
将电子束照射过的膜在非氧化气氛中在450℃下加热90分钟。硅质含氮膜的折射率为1.64。硅质含氮膜的氧含量为24.2质量%。
实施例1至4和对比例1的结果如表1所示。
表1
质均分子量
凝胶渗透色谱法(GPC)使用Alliance e2695高性能GPC系统(Nihon Waters K.K.)和Super Multipore HZ-N GPC柱(Tosoh Corporation)测量。以单分散聚苯乙烯为标准样品,氯仿为洗脱液,在流速0.6mL/min,柱温40℃的条件下进行测定,然后计算质均分子量作为与标准样品相比的相对分子量。
硅、氮和氧含量
使用X射线光电子能谱仪(PHI QuanteraII ULVAC PHI,Inc.)测量硅质含氮膜的硅、氮和氧含量。各元素含量(质量%)是根据硅、氮和氧的总质量计算的。
膜厚和折射率
硅质含氮膜的膜厚和折射率用分光椭偏仪(M-2000V JA WoollamCo.,Inc.)测量。
电击穿场强(Fbd)
使用SSM495 272A-M100(Japan SSM K.K.)测量200nm膜厚的含硅膜的电击穿场强。电流密度超过1E-6(A/cm2)时的电场为Fbd(MV/cm)。
Claims (11)
1.一种制造硅质含氮膜的方法,包括:
(i)将包含聚硅氮烷和溶剂的硅质含氮膜成膜组合物施涂在基材上方以形成涂膜,
(ii)在非氧化气氛中对涂膜照射电子束,
(iii)进行至少一种从由以下构成的群组中选出的工艺:
(a)在非氧化气氛中对电子束照射过的涂膜照射真空紫外光;和
(b)对电子束照射过的涂膜进行等离子体处理,以及
(iv)在非氧化气氛中加热步骤(iii)的处理过的涂膜。
2.根据权利要求1所述的方法,其中该电子束的照射剂量为10MGy至100MGy。
3.根据权利要求1或权利要求2所述的方法,其中该真空紫外光的波长为100至200nm。
4.根据权利要求1至3中任一项所述的方法,其中该聚硅氮烷包含由下式(1)表示的重复单元:
其中R1至R3各自独立地为单键、氢或C1-4烷基。
5.根据权利要求1至4中任一项所述的方法,其中根据聚苯乙烯通过凝胶渗透色谱法测量的聚硅氮烷的质均分子量为900至15,000。
6.根据权利要求1至5中任一项所述的方法,其中该聚硅氮烷是全氢聚硅氮烷。
7.根据权利要求1至6中任一项所述的方法,其中(iv)中的加热在300至800℃下进行。
8.根据权利要求1至7中任一项所述的方法,其中该真空紫外光的照射能量为3至15J/cm2。
9.一种能通过根据权利要求1至8中任一项所述的方法获得的硅质含氮膜。
10.根据权利要求9所述的硅质含氮膜,其中,所述硅质含氮膜的折射率为1.75至2.00。
11.一种制造电子器件的方法,其中该器件包含根据权利要求1至9中任一项所述的硅质含氮膜。
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CN103702933A (zh) * | 2011-06-22 | 2014-04-02 | Az电子材料Ip(日本)株式会社 | 形成氮氧化硅膜的方法和具有由此形成的氮氧化硅膜的衬底 |
EP2871054B1 (en) | 2012-07-06 | 2017-04-05 | Mitsui Chemicals, Inc. | Laminate |
JP2017200861A (ja) * | 2016-05-02 | 2017-11-09 | アーゼッド・エレクトロニック・マテリアルズ(ルクセンブルグ)ソシエテ・ア・レスポンサビリテ・リミテ | 緻密なシリカ質膜形成用組成物 |
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EP4247908A1 (en) | 2023-09-27 |
WO2022106436A1 (en) | 2022-05-27 |
TW202231736A (zh) | 2022-08-16 |
JP7423861B2 (ja) | 2024-01-29 |
KR102584697B1 (ko) | 2023-10-10 |
US20230420244A1 (en) | 2023-12-28 |
KR20230097214A (ko) | 2023-06-30 |
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