JP4049841B2 - Method for forming silicon nitride thin film - Google Patents
Method for forming silicon nitride thin film Download PDFInfo
- Publication number
- JP4049841B2 JP4049841B2 JP35857696A JP35857696A JP4049841B2 JP 4049841 B2 JP4049841 B2 JP 4049841B2 JP 35857696 A JP35857696 A JP 35857696A JP 35857696 A JP35857696 A JP 35857696A JP 4049841 B2 JP4049841 B2 JP 4049841B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- silicon nitride
- thin film
- nitride thin
- polysilazane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims description 30
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims description 30
- 239000010409 thin film Substances 0.000 title claims description 24
- 238000000034 method Methods 0.000 title description 23
- 239000000758 substrate Substances 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 description 46
- 229920001709 polysilazane Polymers 0.000 description 24
- 238000000576 coating method Methods 0.000 description 19
- 239000000126 substance Substances 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 229910007991 Si-N Inorganic materials 0.000 description 7
- 229910006294 Si—N Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- -1 i-heptane Chemical compound 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
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- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000008096 xylene Substances 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
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound 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
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 241001494479 Pecora Species 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004433 infrared transmission spectrum Methods 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229910006293 Si—N—O Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N iso-pentane Natural products CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229930004008 p-menthane Natural products 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
- C04B41/4944—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing atoms other than carbon, hydrogen, oxygen, silicon, alkali metals or halogens, e.g. N-silyldisilazane: Image
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5062—Borides, Nitrides or Silicides
- C04B41/5066—Silicon nitride
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133345—Insulating layers
Description
【０００１】
【発明の属する技術分野】
本発明は、窒化珪素薄膜の形成方法及び同方法により得られる窒化珪素薄膜に関し、詳しくは半導体装置や液晶表示装置における絶縁膜、保護膜などとして、あるいはセラミックスや金属等の表面改質被膜などとして有用な、透明性、緻密性、耐蝕性、耐摩耗性、耐熱性に優れ、且つ耐薬品性に優れた高屈折率を有する高品質の窒化珪素薄膜の形成方法に関する。
【０００２】
【従来の技術】
シリカ、窒化珪素、酸窒化珪素等の珪素質セラミックス薄膜は、その優れた耐熱性、耐摩耗性、耐蝕性等の面から、例えば半導体装置や液晶表示装置における絶縁膜として、あるいは画素電極ないしカラーフィルター上に設けられる保護膜として、利用されている。それらの薄膜の中でも窒化珪素膜は特に不活性雰囲気や還元性雰囲気で高温で安定であり、またシリカ等に比べ高屈折率な透明膜であるという特徴を有する。特に窒化珪素膜は緻密性、高屈折率の点から、近年光デバイスの保護膜、ガスバリア膜として利用されつつある。
このような分野で用いられる珪素質被膜は、一般にＣＶＤ法、スパッタリング法等の気相成長法あるいは珪素質被膜形成用塗布液を用いる塗布法によって基板上に形成されている。ただ、気相成長法によると、手間がかかると共に大きな設備を必要とし、しかも凹凸面上に被膜を形成する場合に凹凸面の平坦化ができない等の問題があるため、近年は塗布法が広く採用されている。
【０００３】
一方、近年、シリカ、窒化珪素、酸窒化珪素の前駆体ポリマーであるポリシラザンが、耐熱性、耐摩耗性、耐蝕性等に優れた珪素質コーティング膜を形成し得るため、注目されており、ポリシラザンを使用する窒化珪素薄膜の形成についても、例えば、特開平１−２０３４７６号、特開平６−４７８６２号各公報等に報告されている。
【０００４】
すなわち、特開平１−２０３４７６号公報には、ポリシラザン含有コーティング組成物を基板に塗布した後、焼成し、窒化珪素からなる被覆膜を形成させるコーティング方法が提案されており、焼成は１００〜１，０００℃（好ましくは２００〜５００℃）の温度範囲で行なわれ、非酸化性雰囲気であれば、Ｓｉ−Ｎ結合の被膜が形成されるとしている。
【０００５】
一方、特開平６−４７８６２号公報には、鋼板（成形体）の表面にポリシラザンからなる被膜を形成する工程と、このポリシラザン被膜を有する鋼板（成形体）を熱処理する工程からなるセラミックス被膜を有する鋼板（成形体）の製造方法が提案されており、ポリシラザン被膜の加熱処理は、空気、不活性ガス、還元性ガスの雰囲気下又は真空下において、１００℃以上（好ましくは２００〜１，３００℃）の温度で行なわれ、加熱処理によりポリシラザン被膜はＳｉ−Ｎ結合やＳｉ−Ｎ−Ｏ結合を有するセラミックス（前駆体）の被膜となるとしている。更に、不活性ガスや還元性雰囲気下での加熱においては、５００℃以上の温度ではポリシラザンの分解が主として起り、Ｓｉ−Ｎ結合を有するセラミックスが形成されると述べられている。
【０００６】
しかし、このようにポリシラザン被膜を不活性ガスや還元性雰囲気下で加熱処理してＳｉ−Ｎ結合を有するセラミックス被膜を得る場合には、ポリシラザンの酸化しやすさのために、環境からの不純物として酸素が膜中に取り込まれ、純粋な窒化珪素膜とならずに酸窒化珪素膜となりやすい。このため純粋な窒化珪素膜を得るためには、１３００℃以上の高温が必要であった。ここで、酸窒化珪素膜は窒化珪素膜に比べ、フッ化水素酸等に対する耐薬品性が劣り、屈折率が低くなるという問題がある。
【０００７】
【発明が解決しようとする課題】
従って、本発明は上記従来技術の実状に鑑みてなされたものであって、耐摩耗性、耐熱性、耐蝕性に優れているのみならず、耐薬品性に優れ且つ高屈折率を有する良好な窒化珪素薄膜の形成方法を提供することをその目的とする。
【０００８】
【課題を解決するための手段】
本発明者は、ポリシラザン塗膜の焼成による窒化珪素薄膜の形成において、より良好な薄膜を得るために鋭意研究を重ねた結果、反応系内における水分が窒化珪素薄膜形成を阻害することを見い出し、本発明に到達した。
【０００９】
すなわち、本発明によれば、ペルヒドロポリシラザン又はその変性物を基材上に塗布した後、真空下に６００℃以上の温度で焼成することを特徴とする窒化珪素薄膜の形成方法が提供される。
【００１０】
なお、本発明によれば、好ましい態様として、下記窒化珪素薄膜及び窒化珪素薄膜の形成方法が提供される。
（１）上記の方法で形成された、５重量％のフッ酸水溶液に対して侵されることがない窒化珪素薄膜。
（２）真空度が０．１Ｐａ以下の雰囲気で焼成すること特徴とする上記の窒化珪素薄膜の形成方法。
【００１１】
本発明の窒化珪素薄膜の形成方法は、ペルヒドロポリシラザン（変性物）を基材に塗布した後、真空下に６００℃以上の温度で焼成するという構成としたことから、本方法によると、反応系内における水分が速やかに除去されるため、ポリシラザンの酸化が抑制され、容易に耐薬品に優れ高屈折率を有する良好な窒化珪素薄膜が得られる。なお、前記特開平６−４７８６２号公報には、ポリシラザン被膜の加熱処理が真空下において行われる場合もある旨記されているが、該公報には本発明の目的は全く認識されておらず、もちろん実施例もない。
【００１２】
【発明の実施の形態】
以下、本発明について詳しく説明する。
本発明では原料ポリシラザンとして、主として下記一般式（Ｉ）
【化１】
【００１３】
上記ペルヒドロポリシラザンの製造方法は、例えば特開昭６０−１４５９０３号公報、Ｄ．ＳｅｙｆｅｒｔｈらＣｏｍｍｕｎｉｃａｔｉｏｎ ｏｆ Ａｍ．Ｃｅｒ．Ｓｏｃ．，Ｃ−１３，Ｊａｎｕａｒｙ １９８３．に報告されている。これらの方法で得られるものは、種々の構造を有するポリマーの混合物であるが、基本的には分子内に鎖状部分と環状部分を含み、
【化２】
【００１４】
ペルヒドロポリシラザンの構造の一例を示すと下記の如くである。
【化３】
また、本発明においては、原料ポリシラザンとして、上記のペルヒドロポリシラザン又は米国特許第４，３９７，８２８号明細書等により開示されたシラザン重合体をトリアルキルアミンの如き第３級アミン類、立体障害性の基を有する第２級アミン類、フォスフィン等の如き塩基性化合物を溶媒とするか又はこれを非塩基性溶媒、例えば、炭化水素類に添加し−７８℃〜３００℃で加熱し脱水縮合反応を行わせることにより得られる数平均分子量２００〜５００，０００、好ましくは５００〜１００，０００の高重合体（特開平１−１３８１０８号公報参照）を用いることもできる。
【００１６】
更に、ペルヒドロポリシラザンの改質反応により得られる重合体で架橋結合−(ＮＨ)−ｎ（ｎ＝１又は２）を有し、珪素原子に結合する窒素と珪素との原子比（Ｎ／Ｓｉ）が０．８以上で数平均分子量が２００〜５００，０００、好ましくは５００〜１００，０００の改質ポリシラザンを用いることもできる。この改質ポリシラザンは、アンモニア又はヒドラジンを使用してポリシラザンの脱水素縮合反応を行わせることにより製造することができる（特開平１−１３８１１０７号公報参照）。
【００１７】
本発明の窒化珪素薄膜の形成方法においては、ペルヒドロポリシラザン（変性物）を基材に塗布した後、該塗膜を真空下に６００℃以上の温度で焼成する。すなわち、まず上記ポリシラザン（変性物）を基材に塗布する処理が行なわれる。該処理に当たっては、上記ポリシラザン（変性物）を有機溶媒に溶解し塗布液を調製する。この場合の有機溶媒としては、特に限定されるものではないが、好ましい具体例としては、次のものが挙げられる。
【００１８】
ベンゼン、トルエン、キシレン、エチルベンゼン、ジエチルベンゼン、トリメチルベンゼン、トリエチルベンゼン等の芳香族化合物；ｎ−ペンタン、ｉ−ペンタン、ｎ−ヘキサン、ｉ−ヘキサン、ｎ−ヘプタン、ｉ−ヘプタン、ｎ−オクタン、ｉ−オクタン、ｎ−ノナン、ｉ−ノナン、ｎ−デカン、ｉ−デカン等の飽和炭化水素化合物；エチルシクロヘキサン、メチルシクロヘキサン、シクロヘキサン、シクロヘキセン、ｐ−メンタン、デカヒドロナフタレン、ジペンテン；ジプロピルエーテル、ジブチルエーテル、ＭＴＢＥ（メチルターシャリーブチルエーテル）等のエーテル類；ＭＩＢＫ等のケトン類など。また、溶剤の蒸発速度の調整のため、適宜これらの溶媒を２種以上混合したものも使用できる。
【００１９】
前記塗布液において、必要に応じて適当な充填剤及び／又は増量剤を加えることができる。充填剤の添加量はペルヒドロポリシラザン（変性物）１重量部に対し、０．０５〜１０重量部の範囲であり、特に好ましい添加量は０．２〜３重量部の範囲である。塗布液には、更に必要に応じて各種顔料、レベリング剤、消泡剤、帯電防止剤、紫外線吸収剤、ｐＨ調整剤、分散剤、表面改質剤、可塑剤、乾燥促進剤、流れ止め剤、等を加えてもよい。
ペルヒドロポリシラザン（変性物）溶解後の濃度は特に限定されるものではないが、通常５〜９５重量％、好ましくは１０〜９０重量％である。
【００２０】
調製された塗布液は、次に基材上に塗布される。基材への塗布は、１回でもよいし、２回以上繰り返し行ってもよい。塗布液を塗布する基材は、特に限定されず、金属、セラミックス、プラスチック等のいずれでもよい。塗布手段としては、通常の塗布方法、つまりスピンコート法、ディップ法、スプレー法、転写法などが用いられる。また、塗布前に基材の脱脂、洗浄等により清浄表面にしておくことで、上記ポリシラザン（変性物）の付着性能が向上する。
【００２１】
基板上に塗布されたペルヒドロポリシラザン（変性物）は、乾燥後、真空中で焼成される。焼成は６００℃以上、好ましくは８００〜１，３００℃の温度で行なわれる。この場合、昇温速度は２００℃／分以下、１℃／分以上、好ましくは１００℃／分以下、５℃／分以上である。真空度は０．１Ｐａ以下、好ましくは０．０１Ｐａ以下、０．０００１Ｐａ以上の範囲で選択される。真空中の焼成処理により、生成水分が迅速に系外に除去され、常圧下における焼成処理と比べて、低温でペルヒドロポリシラザン（変性物）塗膜がＳｉ−Ｎ結合を有する窒化珪素薄膜に変換される。
【００２２】
本発明の方法によって形成された窒化珪素薄膜は、環境から取り込まれる不純物としての酸素が少なく、膜中濃度で２ａｔ％以下となる（不活性雰囲気あるいは還元性雰囲気の常圧下で１３００℃以下で形成される膜中酸素濃度は３〜２０ａｔ％）。そのため、１．９〜２．１という高屈折率を有し（常圧下では１．５〜１．６）、フッ化水素酸に対する耐薬品性を有するという特徴がある。
【００２３】
【実施例】
以下、実施例により本発明を更に詳細に説明するが、本発明の技術的範囲がこれらにより限定されるものではない。
【００２４】
参考例１［ペルヒドロポリシラザンの合成］
内容積１リットルの四つ口フラスコにガス吹き込み管、メカニカルスターラー、ジュワーコンデンサーを装着した。反応器内部を脱酸素した乾燥窒素で置換した後、四つ口フラスコに脱気した乾燥ピリジンを４９０ｍｌ入れ、これを氷冷した。次に、ジクロロシラン５１．９ｇを加えると、白色固体状のアダクト（ＳｉＨ2Ｃｌ2・２Ｃ5Ｈ5Ｎ）が生成した。反応混合物を氷冷し、撹拌しながら水酸化ナトリウム管及び活性炭管を通して精製したアンモニア５１．０ｇを吹き込んだ後、乾燥窒素を液層に吹き込んで未反応のアンモニアを除去した。
【００２５】
反応終了後、反応混合物を遠心分離し、乾燥ピリジンを用いて洗浄した後、更に乾燥窒素雰囲気下で濾過して濾液８５０ｍｌを得た。濾液５ｍｌから溶媒を減圧除去すると、樹脂状固体ペルヒドロポリシラザン０．１０２ｇが得られた。数平均分子量をベンゼンの凝固点降下法で測定したところ、９００であった。
【００２６】
実施例１
参考例１で合成したペルヒドロポリシラザン１０ｇをモレキュラーシープにより十分脱水したキシレン４０ｇに溶解し、２０ｗｔ％のポリシラザン溶液を得た。これをスピンコーターにより清浄なシリコンウェハー上に約０．３μｍ厚に塗布した。このときのスピンコーターの回転条件は４０００ｒｐｍ−２０ｓｅｃであった。この膜を窒素雰囲気下で１００℃のホットプレートで乾燥した後、真空加熱炉で焼成した。焼成条件は９００℃−３０ｍｉｎで、このときの真空度は０．００１Ｐａとした。
【００２７】
得られた膜は、膜厚０．１μｍで、屈折率２．１、赤外透過スペクトルはＳｉ−Ｎ起因のピークのみで、Ｓｉ−Ｈ、Ｎ−Ｈ、Ｓｉ−Ｏピークは見られず、窒化珪素膜となっていることが確認された。この膜の耐薬品性を調べたところ、５ｗｔ％のフッ酸水溶液に対して侵されることなく、十分な耐薬品性を有していることがわかった。
【００２８】
実施例２
参考例１で合成したペルヒドロポリシラザン１０ｇをモレキュラーシーブにより十分脱水したシクロヘキサン９０ｇに溶解し、１０ｗｔ％のポリシラザン溶液を得た。これをディップコートにより清浄なガラス上に約０．３μｍ厚に塗布した。この膜を窒素雰囲気下で１００℃のホットプレートで乾燥した後、真空加熱炉で焼成した。焼成条件は９００℃−３０ｍｉｎで、このときの真空度は０．００１Ｐａとした。
【００２９】
得られた膜は、膜厚０．１μｍで、屈折率２．１であり、この膜の耐薬品性を調べたところ、５ｗｔ％のフッ酸水溶液に侵されることなく、十分な耐薬品性を有していることがわかった。
【００３０】
比較例
参考例１で合成したペルヒドロポリシラザン１０ｇをモレキュラーシープにより十分脱水したキシレン４０ｇに溶解し、２０ｗｔ％のポリシラザン溶液を得た。これをスピンコーターにより清浄なシリコンウェハー上に約０．３μｍ厚に塗布した。このときのスピンコーターの回転条件は４０００ｒｐｍ−２０ｓｅｃあった。この膜を窒素雰囲気下で１００℃のホットプレートで乾燥した後、常圧窒素雰囲気下で焼成した。焼成条件は９００℃−３０ｍｉｎとした。
得られた膜は、膜厚０．２μｍで、屈折率１．６、赤外透過スペクトルはＳｉ−Ｎ起因のピークが主であるが、Ｓｉ−Ｏピークも僅かに観察された。この膜の耐薬品性を調べたところ、５ｗｔ％のフッ酸水溶液に侵され、十分な耐薬品性を有していなかった。
【００３１】
【発明の効果】
請求項１の窒化珪素薄膜の形成方法は、ペルヒドロポリシラザン（変性物）を基材に塗布した後、真空下に６００℃以上の温度で焼成するという構成としたことから、本方法によると、反応系内における水分が速やかに除去され、ポリシラザンの酸化が抑制されるため、容易に耐薬品性に優れ高屈折率を有する良好な窒化珪素薄膜が得られる。
１[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for forming a silicon nitride thin film and a silicon nitride thin film obtained by the method, and more specifically, as an insulating film, a protective film, etc. in a semiconductor device or a liquid crystal display device, or as a surface-modified film such as ceramics or metal. The present invention relates to a method for forming a high-quality silicon nitride thin film having a high refractive index that is excellent in transparency, denseness, corrosion resistance, abrasion resistance, heat resistance, and chemical resistance.
[0002]
[Prior art]
Silicon ceramic thin films such as silica, silicon nitride, silicon oxynitride, etc. are used as insulating films in, for example, semiconductor devices and liquid crystal display devices, or as pixel electrodes or collars in terms of their excellent heat resistance, wear resistance, corrosion resistance, etc. It is used as a protective film provided on the filter. Among these thin films, the silicon nitride film is characterized in that it is stable at a high temperature particularly in an inert atmosphere or a reducing atmosphere and is a transparent film having a higher refractive index than silica or the like. In particular, silicon nitride films are being used as protective films and gas barrier films for optical devices in recent years because of their denseness and high refractive index.
A silicon film used in such a field is generally formed on a substrate by a vapor deposition method such as a CVD method or a sputtering method, or a coating method using a coating solution for forming a silicon film. However, according to the vapor phase growth method, there is a problem that it takes time and requires a large facility, and there is a problem that the uneven surface cannot be flattened when a film is formed on the uneven surface. It has been adopted.
[0003]
On the other hand, in recent years, polysilazane, which is a precursor polymer of silica, silicon nitride, and silicon oxynitride, has been attracting attention because it can form a silicon coating film having excellent heat resistance, wear resistance, corrosion resistance, and the like. The formation of a silicon nitride thin film using a metal is reported, for example, in JP-A-1-203476 and JP-A-6-47862.
[0004]
That is, JP-A-1-203476 proposes a coating method in which a polysilazane-containing coating composition is applied to a substrate and then baked to form a coating film made of silicon nitride. The film is formed in a temperature range of 1,000 ° C. (preferably 200 to 500 ° C.), and a Si—N bond film is formed in a non-oxidizing atmosphere.
[0005]
On the other hand, JP-A-6-47862 has a ceramic film comprising a step of forming a film made of polysilazane on the surface of a steel plate (formed body) and a step of heat-treating the steel sheet (formed body) having this polysilazane film. A method of manufacturing a steel sheet (formed body) has been proposed, and the heat treatment of the polysilazane coating is performed at 100 ° C. or higher (preferably 200 to 1,300 ° C.) in an atmosphere of air, inert gas, reducing gas, or vacuum. The polysilazane coating is formed into a ceramic (precursor) coating having a Si—N bond or a Si—N—O bond by heat treatment. Furthermore, it is stated that in heating in an inert gas or a reducing atmosphere, decomposition of polysilazane mainly occurs at a temperature of 500 ° C. or higher, and ceramics having Si—N bonds are formed.
[0006]
However, when a polysilazane film is heat-treated in an inert gas or a reducing atmosphere to obtain a ceramic film having a Si-N bond, the polysilazane is easily oxidized as an impurity from the environment. Oxygen is taken into the film and is likely to be a silicon oxynitride film instead of a pure silicon nitride film. Therefore, in order to obtain a pure silicon nitride film, a high temperature of 1300 ° C. or higher is necessary. Here, there is a problem that the silicon oxynitride film is inferior in chemical resistance to hydrofluoric acid and the like and has a lower refractive index than the silicon nitride film.
[0007]
[Problems to be solved by the invention]
Therefore, the present invention has been made in view of the actual state of the above-described prior art, and not only has excellent wear resistance, heat resistance, and corrosion resistance, but also has excellent chemical resistance and a high refractive index. It is an object of the present invention to provide a method for forming a silicon nitride thin film.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to obtain a better thin film in the formation of a silicon nitride thin film by baking a polysilazane coating film, the present inventors have found that moisture in the reaction system inhibits the formation of the silicon nitride thin film, The present invention has been reached.
[0009]
That is, according to the present invention, there is provided a method for forming a silicon nitride thin film, wherein perhydropolysilazane or a modified product thereof is applied on a substrate and then baked at a temperature of 600 ° C. or higher under vacuum. .
[0010]
In addition, according to this invention, the formation method of the following silicon nitride thin film and silicon nitride thin film is provided as a preferable aspect.
(1) A silicon nitride thin film formed by the above method and not attacked by a 5 wt% hydrofluoric acid aqueous solution.
(2) The method for forming a silicon nitride thin film as described above, wherein firing is performed in an atmosphere having a degree of vacuum of 0.1 Pa or less.
[0011]
The method for forming a silicon nitride thin film of the present invention has a structure in which perhydropolysilazane (modified product) is applied to a substrate and then baked at a temperature of 600 ° C. or higher under vacuum. Since water in the system is quickly removed, oxidation of polysilazane is suppressed, and a good silicon nitride thin film having excellent chemical resistance and high refractive index can be easily obtained. In addition, in the above-mentioned JP-A-6-47862, it is noted that the heat treatment of the polysilazane film may be performed under vacuum, but the purpose of the present invention is not recognized at all in the publication, Of course, there is no embodiment.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
In the present invention, the raw material polysilazane is mainly represented by the following general formula (I)
[Chemical 1]
[0013]
The method for producing the perhydropolysilazane is disclosed in, for example, JP-A-60-145903, D.C. Seyferth et al. Communication of Am. Cer. Soc. , C-13, January 1983. Has been reported. What is obtained by these methods is a mixture of polymers having various structures, but basically includes a chain portion and a cyclic portion in the molecule,
[Chemical 2]
[0014]
An example of the structure of perhydropolysilazane is as follows.
[Chemical 3]
In the present invention, the perhydropolysilazane or the silazane polymer disclosed in US Pat. No. 4,397,828 is used as a starting polysilazane, a tertiary amine such as a trialkylamine, a steric hindrance. A secondary compound having a functional group, a basic compound such as phosphine or the like, or a non-basic solvent such as a hydrocarbon, and heating at −78 ° C. to 300 ° C. for dehydration condensation A high polymer (see JP-A-1-138108) having a number average molecular weight of 200 to 500,000, preferably 500 to 100,000, obtained by carrying out the reaction can also be used.
[0016]
Further, a polymer obtained by a modification reaction of perhydropolysilazane, which has a crosslink bond — (NH) —n (n = 1 or 2), and an atomic ratio of nitrogen to silicon bonded to silicon atoms (N / Si) ) Is 0.8 or more, and a modified polysilazane having a number average molecular weight of 200 to 500,000, preferably 500 to 100,000 can also be used. This modified polysilazane can be produced by performing a dehydrogenative condensation reaction of polysilazane using ammonia or hydrazine (see Japanese Patent Laid-Open No. 1-181107).
[0017]
In the method for forming a silicon nitride thin film of the present invention, after applying perhydropolysilazane (modified product) to a substrate, the coating film is baked at a temperature of 600 ° C. or higher under vacuum. That is, first, a process of applying the polysilazane (modified product) to a substrate is performed. In the treatment, the polysilazane (modified product) is dissolved in an organic solvent to prepare a coating solution. The organic solvent in this case is not particularly limited, but preferred specific examples include the following.
[0018]
Aromatic compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene; n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, n-octane, i -Saturated hydrocarbon compounds such as octane, n-nonane, i-nonane, n-decane, i-decane; ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexene, p-menthane, decahydronaphthalene, dipentene; dipropyl ether, di Ethers such as butyl ether and MTBE (methyl tertiary butyl ether); ketones such as MIBK. Further, in order to adjust the evaporation rate of the solvent, a mixture of two or more of these solvents can be used as appropriate.
[0019]
In the coating solution, an appropriate filler and / or extender can be added as necessary. The addition amount of the filler is in the range of 0.05 to 10 parts by weight with respect to 1 part by weight of perhydropolysilazane (modified product), and the particularly preferable addition amount is in the range of 0.2 to 3 parts by weight. For the coating solution, various pigments, leveling agents, antifoaming agents, antistatic agents, UV absorbers, pH adjusters, dispersants, surface modifiers, plasticizers, drying accelerators, and flow inhibitors are added as necessary. , Etc. may be added.
The concentration after dissolution of perhydropolysilazane (modified product) is not particularly limited, but is usually 5 to 95% by weight, preferably 10 to 90% by weight.
[0020]
The prepared coating solution is then applied onto the substrate. The application to the substrate may be performed once or may be repeated twice or more. The base material to which the coating solution is applied is not particularly limited, and may be any of metal, ceramics, plastic, and the like. As a coating means, a normal coating method, that is, a spin coating method, a dip method, a spray method, a transfer method, or the like is used. Moreover, the adhesion performance of the said polysilazane (modified | denatured substance) improves by making it a clean surface by degreasing, washing | cleaning, etc. of a base material before application | coating.
[0021]
The perhydropolysilazane (modified product) applied on the substrate is dried and then baked in vacuum. Firing is performed at a temperature of 600 ° C. or higher, preferably 800 to 1,300 ° C. In this case, the heating rate is 200 ° C./min or less, 1 ° C./min or more, preferably 100 ° C./min or less, 5 ° C./min or more. The degree of vacuum is selected in the range of 0.1 Pa or less, preferably 0.01 Pa or less, 0.0001 Pa or more. The generated moisture is quickly removed from the system by baking in vacuum, and the perhydropolysilazane (modified) coating film is converted to a silicon nitride thin film having Si-N bonds at a lower temperature compared to baking under normal pressure. Is done.
[0022]
The silicon nitride thin film formed by the method of the present invention has less oxygen as an impurity taken in from the environment, and the concentration in the film is 2 at% or less (formed at 1300 ° C. or less under normal pressure in an inert atmosphere or a reducing atmosphere). The oxygen concentration in the film is 3 to 20 at %). Therefore, it has a high refractive index of 1.9 to 2.1 (1.5 to 1.6 under normal pressure) and is characterized by having chemical resistance against hydrofluoric acid.
[0023]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, the technical scope of this invention is not limited by these.
[0024]
Reference Example 1 [Synthesis of perhydropolysilazane]
A four-necked flask with an internal volume of 1 liter was equipped with a gas blowing tube, a mechanical stirrer, and a dewar condenser. After replacing the inside of the reactor with deoxygenated dry nitrogen, 490 ml of degassed dry pyridine was placed in a four-necked flask and cooled on ice. Next, when 51.9 g of dichlorosilane was added, a white solid adduct (SiH 2 Cl 2 .2C 5 H 5 N) was produced. The reaction mixture was ice-cooled, and 51.0 g of purified ammonia was blown through a sodium hydroxide tube and an activated carbon tube while stirring, and then dry nitrogen was blown into the liquid layer to remove unreacted ammonia.
[0025]
After completion of the reaction, the reaction mixture was centrifuged, washed with dry pyridine, and further filtered under a dry nitrogen atmosphere to obtain 850 ml of a filtrate. When the solvent was removed under reduced pressure from 5 ml of the filtrate, 0.102 g of resinous solid perhydropolysilazane was obtained. The number average molecular weight was 900 as measured by the freezing point depression method of benzene.
[0026]
Example 1
10 g of perhydropolysilazane synthesized in Reference Example 1 was dissolved in 40 g of xylene sufficiently dehydrated by molecular sheep to obtain a 20 wt% polysilazane solution. This was applied on a clean silicon wafer to a thickness of about 0.3 μm by a spin coater. The rotation condition of the spin coater at this time was 4000 rpm-20 sec. This film was dried on a hot plate at 100 ° C. in a nitrogen atmosphere, and then baked in a vacuum heating furnace. Firing conditions were 900 ° C.-30 min, and the degree of vacuum at this time was 0.001 Pa.
[0027]
The obtained film had a thickness of 0.1 μm, a refractive index of 2.1, and an infrared transmission spectrum with only Si-N-derived peaks, and no Si-H, NH, or Si-O peaks were observed. It was confirmed to be a silicon nitride film. When the chemical resistance of this film was examined, it was found that the film had sufficient chemical resistance without being attacked by a 5 wt% hydrofluoric acid aqueous solution.
[0028]
Example 2
10 g of perhydropolysilazane synthesized in Reference Example 1 was dissolved in 90 g of cyclohexane sufficiently dehydrated by molecular sieve to obtain a 10 wt% polysilazane solution. This was applied on a clean glass to a thickness of about 0.3 μm by dip coating. This film was dried on a hot plate at 100 ° C. in a nitrogen atmosphere, and then baked in a vacuum heating furnace. Firing conditions were 900 ° C.-30 min, and the degree of vacuum at this time was 0.001 Pa.
[0029]
The obtained film had a thickness of 0.1 μm and a refractive index of 2.1. When chemical resistance of this film was examined, sufficient chemical resistance was obtained without being attacked by a 5 wt% hydrofluoric acid aqueous solution. I found it.
[0030]
Comparative Example 10 g of perhydropolysilazane synthesized in Reference Example 1 was dissolved in 40 g of xylene sufficiently dehydrated by molecular sheep to obtain a 20 wt% polysilazane solution. This was applied on a clean silicon wafer to a thickness of about 0.3 μm by a spin coater. The rotation condition of the spin coater at this time was 4000 rpm-20 sec. The film was dried on a hot plate at 100 ° C. in a nitrogen atmosphere and then fired in a normal pressure nitrogen atmosphere. The firing conditions were 900 ° C.-30 min.
The obtained film had a film thickness of 0.2 μm, a refractive index of 1.6, and an infrared transmission spectrum mainly having a peak due to Si—N, but a slight Si—O peak was also observed. When the chemical resistance of this film was examined, it was affected by a 5 wt% hydrofluoric acid aqueous solution and did not have sufficient chemical resistance.
[0031]
【The invention's effect】
Since the method for forming a silicon nitride thin film according to claim 1 has a structure in which perhydropolysilazane (modified product) is applied to a substrate and then fired at a temperature of 600 ° C. or higher under vacuum, according to the present method, Since moisture in the reaction system is quickly removed and oxidation of polysilazane is suppressed, a good silicon nitride thin film having excellent chemical resistance and high refractive index can be easily obtained.
1
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35857696A JP4049841B2 (en) | 1996-12-27 | 1996-12-27 | Method for forming silicon nitride thin film |
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| Application Number | Priority Date | Filing Date | Title |
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| JP35857696A JP4049841B2 (en) | 1996-12-27 | 1996-12-27 | Method for forming silicon nitride thin film |
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| JPH10194873A JPH10194873A (en) | 1998-07-28 |
| JP4049841B2 true JP4049841B2 (en) | 2008-02-20 |
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| JP35857696A Expired - Lifetime JP4049841B2 (en) | 1996-12-27 | 1996-12-27 | Method for forming silicon nitride thin film |
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Cited By (1)
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|---|---|---|---|---|
| WO2022106436A1 (en) | 2020-11-20 | 2022-05-27 | Merck Patent Gmbh | Method of manufacturing silicon nitrogeneous film |
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| JP2008108753A (en) * | 2005-02-10 | 2008-05-08 | Az Electronic Materials Kk | Semiconductor device having silicon nitride film derived from polysilazane and its fabrication process |
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| KR102294031B1 (en) | 2018-10-26 | 2021-08-27 | 주식회사 엘지화학 | A barrier film |
| KR102294026B1 (en) | 2018-10-26 | 2021-08-27 | 주식회사 엘지화학 | A barrier film |
| KR102294027B1 (en) | 2018-10-26 | 2021-08-27 | 주식회사 엘지화학 | A barrier film |
| CN114761229A (en) * | 2019-12-05 | 2022-07-15 | 株式会社小糸制作所 | Resin molded article, resin molded article for vehicle window, and method for producing resin molded article |
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1996
- 1996-12-27 JP JP35857696A patent/JP4049841B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022106436A1 (en) | 2020-11-20 | 2022-05-27 | Merck Patent Gmbh | Method of manufacturing silicon nitrogeneous film |
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| JPH10194873A (en) | 1998-07-28 |
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