JP4640745B2 - Raw material for chemical vapor deposition and method for producing ceramics using the same - Google Patents
Raw material for chemical vapor deposition and method for producing ceramics using the same Download PDFInfo
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- JP4640745B2 JP4640745B2 JP2001151553A JP2001151553A JP4640745B2 JP 4640745 B2 JP4640745 B2 JP 4640745B2 JP 2001151553 A JP2001151553 A JP 2001151553A JP 2001151553 A JP2001151553 A JP 2001151553A JP 4640745 B2 JP4640745 B2 JP 4640745B2
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- raw material
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- compound
- chemical vapor
- vapor deposition
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- 239000002994 raw material Substances 0.000 title claims description 47
- 238000005229 chemical vapour deposition Methods 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000000919 ceramic Substances 0.000 title claims description 20
- 150000002736 metal compounds Chemical class 0.000 claims description 16
- 239000005304 optical glass Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 37
- 238000000151 deposition Methods 0.000 description 22
- 239000007789 gas Substances 0.000 description 19
- -1 alkoxide compound Chemical class 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 230000008021 deposition Effects 0.000 description 13
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000002184 metal Substances 0.000 description 8
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
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- 239000002019 doping agent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
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- 238000004891 communication Methods 0.000 description 3
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- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 239000002585 base Substances 0.000 description 2
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- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 235000015067 sauces Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
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- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
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- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 description 2
- BGYBONWLWSMGNV-UHFFFAOYSA-N 1,4,7,10,13,16,19,22-octaoxacyclotetracosane Chemical compound C1COCCOCCOCCOCCOCCOCCOCCO1 BGYBONWLWSMGNV-UHFFFAOYSA-N 0.000 description 1
- QBPPRVHXOZRESW-UHFFFAOYSA-N 1,4,7,10-tetraazacyclododecane Chemical compound C1CNCCNCCNCCN1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 description 1
- MDAXKAUIABOHTD-UHFFFAOYSA-N 1,4,8,11-tetraazacyclotetradecane Chemical compound C1CNCCNCCCNCCNC1 MDAXKAUIABOHTD-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
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- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- JTBKFHQUYVNHSR-UHFFFAOYSA-N propan-2-yloxyalumane Chemical compound CC(C)O[AlH2] JTBKFHQUYVNHSR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ACOVYJCRYLWRLR-UHFFFAOYSA-N tetramethoxygermane Chemical compound CO[Ge](OC)(OC)OC ACOVYJCRYLWRLR-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- NKLYMYLJOXIVFB-UHFFFAOYSA-N triethoxymethylsilane Chemical compound CCOC([SiH3])(OCC)OCC NKLYMYLJOXIVFB-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- GYTROFMCUJZKNA-UHFFFAOYSA-N triethyl triethoxysilyl silicate Chemical compound CCO[Si](OCC)(OCC)O[Si](OCC)(OCC)OCC GYTROFMCUJZKNA-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- XOAJIYVOSJHEQB-UHFFFAOYSA-N trimethyl trimethoxysilyl silicate Chemical compound CO[Si](OC)(OC)O[Si](OC)(OC)OC XOAJIYVOSJHEQB-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- LYRCQNDYYRPFMF-UHFFFAOYSA-N trimethyltin Chemical compound C[Sn](C)C LYRCQNDYYRPFMF-UHFFFAOYSA-N 0.000 description 1
- OXFUXNFMHFCELM-UHFFFAOYSA-N tripropan-2-yl phosphate Chemical compound CC(C)OP(=O)(OC(C)C)OC(C)C OXFUXNFMHFCELM-UHFFFAOYSA-N 0.000 description 1
- SJHCUXCOGGKFAI-UHFFFAOYSA-N tripropan-2-yl phosphite Chemical compound CC(C)OP(OC(C)C)OC(C)C SJHCUXCOGGKFAI-UHFFFAOYSA-N 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2207/00—Glass deposition burners
- C03B2207/30—For glass precursor of non-standard type, e.g. solid SiH3F
- C03B2207/32—Non-halide
Description
【０００１】
【発明の属する技術分野】
本発明は、特定の分子構造を有する金属化合物を含有してなる化学気相成長（以下、ＣＶＤと記載することもある）用原料及びこれを用いたセラミックスの製造方法に関し、詳しくは、特定の分子構造を有するチタニウムの化合物を含有してなるＣＶＤ用原料及びこれを用いたＣＶＤ法によるセラミックスの製造方法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
チタニウム、ゲルマニウム、ジルコニウム、スズ、ハフニウム、鉛の４価金属元素及び珪素を含む機能性セラミックスは、特異な機械的特性、電気特性、光学特性を有するので、半導体、電子部品、光学部品等に応用が期待されており、特に珪酸系光学ガラスを用いた高速大容量通信システムを実現するものとして期待されている。
【０００３】
珪酸系光学ガラスを用いた光通信システムの部材としては、レーザ発信器、光ファイバ、光導波路、光増幅器、光スイッチ等が挙げられる。例えば、チタニウム、ゲルマニウム、スズから選ばれる元素をドープした珪酸系光学ガラスは、光ファイバ、光導波路、光スイッチに応用されている。
【０００４】
これら珪酸系光学ガラスを含む機能性セラミックスの製造法としては、火焔堆積法、スパッタリング法、イオンプレーティング法、塗布熱分解法やゾルゲル法等のＭＯＤ法が挙げられるが、組成制御性、段差被覆性に優れること、半導体デバイスと類似のプロセスを用いることが可能で量産化に適すること、ハイブリッド集積が可能である等の多くの長所を有しているので、化学気相成長（ＣＶＤ）法が最適な製造プロセスである。
【０００５】
ゲルマニウム、スズのＣＶＤ用原料としては、例えば、工業材料２０００年７月号（Ｖｏｌ．４８ Ｎｏ．７）、特開平９−１３３８２７号公報、特開平１１−２７１５５３号公報、特開２０００−２２７５２５号公報等でテトラメトキシゲルマニウム等のテトラアルコキシゲルマニウムやトリメチルスズが報告されており、また、チタニウムのＣＶＤ用原料としては、例えば、特開平５−９７３８号公報、特開平５−２７１２５３号公報、特開平１０−１１４７８１号公報等にアルコキシド化合物、β−ジケトネート等が報告されている。
【０００６】
しかし、上記のＣＶＤ用原料は、多成分系のセラミックスを製造する場合に、他成分のＣＶＤ用原料と蒸気圧や分解特性等が異なるために、均質なセラミックスを得られない場合がある。例えば、珪酸系光学ガラスを製造する場合は、母材である珪酸系ガラス中にドーパントが局在化して得られる珪酸系光学ガラス層の不均質化や異常成長の問題がある。
【０００７】
従って、本発明の目的は、化学気相成長（ＣＶＤ）法において、組成制御が容易であり、ドーパントの局在化を抑制できる化学気相成長（ＣＶＤ）用原料及びこれを用いたセラミックスの製造方法を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者等は、検討を重ねた結果、特定の金属化合物をＣＶＤ用原料として用いることにより、ドーパントの局在化を抑制できることを知見し、本発明に到達した。
【０００９】
本発明は、上記知見に基づいてなされたものであり、下記一般式（Ｉ）で表される金属化合物を含有してなる化学気相成長用原料及びこれを用いたセラミックスの製造方法を提供するものである。
【化２】
【００１０】
【発明の実施の形態】
以下、本発明の実施形態について詳細に説明する。
【００１１】
本発明に係る上記一般式（Ｉ）で表される金属化合物において、Ｒで表される炭素数１〜８のアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、第二ブチル、第三ブチル、イソブチル、アミル、イソアミル、第三アミル、ヘキシル、シクロヘキシル、ヘプチル、イソヘプチル、第三ヘプチル、ｎ−オクチル、イソオクチル、第三オクチル、２−エチルヘキシルが挙げられる。
【００１２】
本発明に係る上記一般式（Ｉ）で表される金属化合物の具体例としては、例えば、下記に例示する化合物Ｎｏ．１〜４が挙げられる。
【００１３】
【化３】
本発明に係る上記一般式（Ｉ）で表される金属化合物は、その製造方法において、特に制限を受けることはない。該製造方法としては、例えば、４価の金属元素（チタニウム）の塩化物、硝酸塩、硫酸塩等の無機塩又はその水和物と、該当する構造のトリアルキルシラノールとを水酸化ナトリウム、アンモニア、アミン等の塩基の存在下で反応させて製造する方法、４価の金属元素の無機塩又はその水和物と、トリアルキルシリルオキシナトリウム等のトリアルキルシラノールとアルカリ金属のアルコキシド化合物とを反応させて製造する方法、４価の金属元素のテトラメトキシド、テトラエトキシド、テトライソプロポキシド、テトラブトキシド等の低分子アルコールのアルコキシドとトリアルキルシラノールとの交換反応により製造する方法が挙げられる。
【００１５】
本発明の化学気相成長（ＣＶＤ）用原料とは、上記の金属化合物を含有してなるものであり、その形態は、使用されるＣＶＤ法の輸送供給方法等の手法により適宜選択されるものである。
【００１６】
輸送供給方法としては、ＣＶＤ用原料を原料容器中で加熱及び／又は減圧することにより気化させ、必要に応じて用いられるアルゴン、窒素、ヘリウム等のキャリアガスと共に堆積反応部へと導入する気体輸送法、ＣＶＤ用原料を液体又は溶液の状態で気化室まで輸送し、気化室で加熱及び／又は減圧することにより気化させて、堆積反応部へと導入する液体輸送法がある。気体輸送法の場合は、上記の金属化合物そのものがＣＶＤ用原料となり、液体輸送法の場合は、該金属化合物そのもの又は該金属化合物を有機溶剤に溶かした金属化合物溶液がＣＶＤ用原料となる。
【００１７】
また、多成分系薄膜を製造する多成分系のＣＶＤ法においては、ＣＶＤ用原料を各成分独立で供給する方法（以下、シングルソース法と記載することもある）と、多成分原料を予め所望の組成で混合した混合原料を供給する方法（以下、カクテルソース法と記載することもある）がある。カクテルソース法の場合、本発明に係る金属化合物と他の成分の金属供給源化合物との混合物或いは混合溶液がＣＶＤ用原料である。
【００１８】
上記のＣＶＤ用原料に使用する有機溶剤としては、特に制限を受けることはなく周知一般の有機溶剤を用いることができる。該有機溶剤としては、例えば、メタノール、エタノール、２−プロパノール、ｎ−ブタノール等のアルコール類；酢酸エチル、酢酸ブチル、酢酸メトキシエチル等の酢酸エステル類、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル等のエーテルアルコール類；テトラヒドロフラン、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、ジブチルエーテル等のエーテル類；メチルブチルケトン、メチルイソブチルケトン、エチルブチルケトン、ジプロピルケトン、ジイソブチルケトン、メチルアミルケトン、シクロヘキサノン、メチルシクロヘキサノン等のケトン類；ヘキサン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、ヘプタン、オクタン、トルエン、キシレン等の炭化水素類が挙げられ、これらは、溶質の溶解性、使用温度と沸点、引火点の関係等によって適宜選択される。
【００１９】
上記の他の成分の金属供給源化合物としては、特に制限を受けず周知一般のＣＶＤ原料となる化合物を用いることができる。該金属供給源化合物としては、アルコール化合物、グリコール化合物、β−ジケトン化合物、シクロペンタジエン化合物等の１種類又は２種類以上の有機配位化合物と金属との化合物が挙げられる。
【００２０】
上記の他の成分の金属供給源化合物としては、例えば、珪酸系光学ガラスを製造する場合は、珪素化合物としては、モノシラン、ジシラン、トリメチルシラン、トリエチルシラン、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトライソプロポキシシラン、テトラブトキシシラン、オクタメチルシクロテトラシロキサン、ヘキサメトキシジシロキサン、ヘキサエトキシジシロキサン、トリメトキシメチルシラン、トリエトキシメチルシラン、トリメチルメトキシシラン、トリメチルエトキシシラン、ヘキサメチルジシロキサン等が挙げられ、硼素化合物としては、ボラン、ジボラン、トリメチルボレート、トリエチルボレート、トリメチル硼素、トリエチル硼素等が挙げられ、リン化合物としては、トリメチルホスフェート、トリエチルホスフェート、トリプロピルホスフェート、トリイソプロピルホスフェート、トリブチルホスフェート、トリメチルホスファイト、トリエチルホスファイト、トリプロピルホスファイト、トリイソプロピルホスファイト等が挙げられ、珪素−硼素化合物及び珪素−リン化合物としては、特開平２−１２９１６号公報に記載のトリス（トリメチルシリル）ボレート、ジメチル（トリメチルシリル）ホスファイト等が挙げられ、アルミニウム化合物としては、トリメチルアルミニウム、トリエチルアルミニウム、トリブチルアルミニウム、トリメトキシアルミニウム、トリエトキシアルミニウム、トリイソプロポキシアルミニウム、トリス（２，２，６，６−テトラメチルヘプタン−３，５−ジオナト）アルミニウム等が挙げられ、希土類化合物としては、ランタン、プラセオジム、エルビウム、ツリウムのβ−ジケトン錯体等が挙げられる。
【００２１】
本発明のＣＶＤ用原料には、必要に応じて金属化合物の安定性を付与するため求核性試薬を含有してもよい。該求核試薬としては、グライム、ジグライム、トリグライム、テトラグライム等のエチレングリコールエーテル類、１８−クラウン−６、ジシクロヘキシル−１８−クラウン−６、２４−クラウン−８、ジシクロヘキシル−２４−クラウン−８、ジベンゾ−２４−クラウン−８等のクラウンエーテル類、エチレンジアミン、Ｎ, Ｎ’−テトラメチルエチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、１，１，４，７，７−ペンタメチルジエチレントリアミン、１，１，４，７，１０，１０−ヘキサメチルトリエチレンテトラミン等のポリアミン類、サイクラム、サイクレン等の環状ポリアミン類、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸−２−メトキシエチル等のβ−ケトエステル類又はβ−ジケトン類が挙げられ、これら安定剤の使用量は、金属化合物１モルに対して０．１モル〜１０モルの範囲で使用され、好ましくは１〜４モルで使用される。
【００２２】
本発明のセラミックスの製造方法とは、上記説明のＣＶＤ用原料を用いた化学気相成長（ＣＶＤ）法によるものである。ＣＶＤ法とは、気化させた原料と必要に応じて用いられる反応性ガスを基板上に導入し、次いで、原料を基板上で分解及び／又は反応させてセラミックスを基板上に成長、堆積させる方法を指す。本発明の製造方法は、原料の輸送供給方法、堆積方法、製造条件、製造装置等については、特に制限を受けるものではなく、周知一般の条件、方法を用いることができる。
【００２３】
上記の必要に応じて用いられる反応性ガスとしては、例えば、酸素、オゾン、二酸化窒素、一酸化窒素等が挙げられる。
【００２４】
また、上記の輸送供給方法としては、上記に記載の気体輸送法、液体輸送法、シングルソース法、カクテルソース法等が挙げられる。
【００２５】
また、上記の堆積方法としては、原料ガス又は原料ガスと反応性ガスを熱のみにより反応させセラミックスを堆積させる熱ＣＶＤ、熱とプラズマを使用するプラズマＣＶＤ、熱と光を使用する光ＣＶＤ、熱、光及びプラズマを使用する光プラズマＣＶＤが挙げられる。
【００２６】
また、上記の製造条件としては、反応温度（基板温度）、反応圧力、堆積速度等が挙げられる。反応温度については、原料である本発明に係る上記の金属化合物が充分に反応する温度である２００℃以上が好ましく、３５０〜８００℃がより好ましい。また、反応圧力は、熱ＣＶＤ、光ＣＶＤの場合、大気圧〜１００Ｐａが好ましく、プラズマを使用する場合は、１００〜２０００Ｐａが好ましい。また、堆積速度は、原料の供給条件（気化温度、気化圧力）、反応温度、反応圧力によりコントロールすることができる。堆積速度は、大きいと得られるセラミックスの特性が悪化する場合があり、小さいと生産性効率に問題を生じる場合があるので、２０〜１０００ｎｍ／分が好ましく、５０〜５００ｎｍ／分がより好ましい。
【００２７】
また、本発明のセラミックスの製造方法においては、段差埋め込みが必要な場合は、セラミックス層堆積の後にリフロー工程を設けてもよい。この場合にリフロー温度は、６００〜１２００℃であり、７００〜１０００℃が好ましい。
【００２８】
本発明のＣＶＤ原料及びこれを用いたセラミックスの製造方法は、光通信システムの部材である光ファイバ、光導波路、光増幅器、光スイッチ等に使用される珪酸系光学ガラスの製造に特に好適に使用されるものである。該珪酸系光学ガラスとしては、酸化珪素と必要に応じて含有される酸化アルミニウム、酸化硼素、酸化リン、希土類元素（ランタン、プラセオジム、エルビウム、ツリウム等）の酸化物等からなる珪酸系ガラスに酸化チタニウム、酸化ゲルマニウム、酸化ジルコニウム、酸化スズ、酸化ハフニウム、酸化鉛から選ばれる１種以上をドープしたものが挙げられる。また、これら珪酸系光学ガラス中のＭで表される金属元素のモル比は、珪素元素１００に対して０．１〜２５が好ましく、１〜１５がより好ましい。
【００２９】
【実施例】
以下、実施例、比較例及び評価例をもって本発明を更に詳細に説明する。しかしながら、本発明は以下の実施例、比較例及び評価例によって何ら制限を受けるものではない。
【００３０】
〔実施例１〕
以下の方法、条件によるＣＶＤ法により、６インチのシリコンウエハ上に２０μｍの珪酸系光学ガラス層を堆積させた供試試料を製造した。以下の実施例及び比較例も同様である。
原料（温度）：化合物Ｎｏ．１（７５℃）
原料輸送供給方法：気体輸送、シングルソース
堆積方法：熱ＣＶＤ
反応性ガス：オゾン、酸素
反応圧力：４００〜８００Ｐａ
基板温度：４５０℃
堆積速度：１５０ｎｍ／分
【００３１】
〔実施例２〕
原料（温度）：化合物Ｎｏ．１（１１０℃）、ヘキサメチルジシロキサン（１０℃）
原料輸送供給方法：気体輸送、シングルソース
堆積方法：熱ＣＶＤ
反応性ガス：オゾン、酸素
反応圧力：大気圧
基板温度：４５０℃
堆積速度：１７０ｎｍ／分
【００３２】
〔実施例３〕
原料（温度）：化合物Ｎｏ．１（１００℃）、テトラエトキシシラン（５５℃）
原料輸送供給方法：気体輸送、シングルソース
堆積方法：熱ＣＶＤ
反応性ガス：オゾン、酸素
反応圧力：８００〜１０００Ｐａ
基板温度：４５０℃
堆積速度：２１０ｎｍ／分
【００３３】
〔実施例４〕
原料（温度）：化合物Ｎｏ．１（１００℃）、ヘキサメチルジシロキサン（１０℃）
原料輸送供給方法：気体輸送、シングルソース
堆積方法：熱ＣＶＤ
反応性ガス：オゾン、酸素
反応圧力：１０００〜１２００Ｐａ
基板温度：４５０℃
堆積速度：２２０ｎｍ／分
【００３４】
〔実施例５〕
原料（温度）：化合物Ｎｏ．１（７５℃）、トリス（トリメチルシリル）ボレート（３０℃）
原料輸送供給方法：気体輸送、シングルソース
堆積方法：熱ＣＶＤ
反応性ガス：オゾン、酸素
反応圧力：４００〜８００Ｐａ
基板温度：４５０℃
堆積速度：１７０ｎｍ／分
【００３８】
〔比較例１〕
原料（温度）：テトライソプロポキシチタン（５５℃）、テトラエトキシシラン（６５℃）
原料輸送供給方法：気体輸送、シングルソース
堆積方法：熱ＣＶＤ
反応性ガス：オゾン、酸素
反応圧力：６００〜１０００Ｐａ
基板温度：４５０℃
堆積速度：１８０ｎｍ／分
【００４０】
〔評価例〕
上記の実施例及び比較例で得た供試試料について、それぞれ同一箇所（４箇所）をエネルギー分散形Ｘ線分析法（ＥＤＸ）による元素分析を行った。４箇所中で組成比のずれが一番の大きい組み合わせの２箇所（ポイントＡ、ポイントＢ）の比較により組成のばらつきを評価した。ばらつきは、珪素のモル数を１００とした各検出元素の割合で示した。結果を表１及び２に示す。
【００４１】
【表１】
【表２】
【発明の効果】
本発明は、ＣＶＤ法において、組成制御が容易であり、ドーパントの局在化を抑制できるＣＶＤ用原料及びこれを用いたセラミックスの製造方法を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a raw material for chemical vapor deposition (hereinafter sometimes referred to as CVD) containing a metal compound having a specific molecular structure, and a method for producing ceramics using the same. the method of manufacturing a ceramic by a CVD material comprising the compound of Chitaniu beam having a molecular structure and a CVD method using the same.
[0002]
[Prior art and problems to be solved by the invention]
Functional ceramics containing titanium, germanium, zirconium, tin, hafnium, lead tetravalent metal elements and silicon have unique mechanical, electrical, and optical properties, so they can be applied to semiconductors, electronic components, optical components, etc. In particular, it is expected to realize a high-speed and large-capacity communication system using silicate optical glass.
[0003]
Examples of the members of the optical communication system using the silicate optical glass include a laser transmitter, an optical fiber, an optical waveguide, an optical amplifier, and an optical switch. For example, silicate optical glass doped with an element selected from titanium, germanium, and tin is applied to optical fibers, optical waveguides, and optical switches.
[0004]
Examples of methods for producing functional ceramics containing these silicate optical glasses include flame deposition methods, sputtering methods, ion plating methods, coating pyrolysis methods, sol-gel methods, and other MOD methods. The chemical vapor deposition (CVD) method has many advantages such as being excellent in performance, being able to use a process similar to a semiconductor device, suitable for mass production, and capable of hybrid integration. It is an optimal manufacturing process.
[0005]
As a raw material for CVD of germanium and tin, for example, July 2000 (Vol. 48 No. 7) of industrial materials, JP-A-9-133828, JP-A-11-271553, JP-A-2000-227525. Tetraalkoxygermanium such as tetramethoxygermanium and trimethyltin are reported in Gazettes and the like, and as a CVD raw material for titanium, for example, JP-A-5-9738, JP-A-5-271253, An alkoxide compound, β-diketonate, and the like are reported in JP-A-10-114781 and the like.
[0006]
However, when the above-mentioned CVD raw material is used to produce multi-component ceramics, there is a case where homogeneous ceramics cannot be obtained due to differences in vapor pressure, decomposition characteristics, and the like from the CVD raw materials of other components. For example, when manufacturing a silicate type optical glass, there exists a problem of the heterogeneity of the silicate type | system | group optical glass layer obtained by localizing a dopant in the silicate type glass which is a base material, and abnormal growth.
[0007]
Accordingly, an object of the present invention is to provide a chemical vapor deposition (CVD) raw material capable of easily controlling composition and suppressing dopant localization in a chemical vapor deposition (CVD) method, and manufacturing a ceramic using the raw material. It is to provide a method.
[0008]
[Means for Solving the Problems]
As a result of repeated studies, the present inventors have found that localization of dopants can be suppressed by using a specific metal compound as a raw material for CVD, and have reached the present invention.
[0009]
The present invention has been made based on the above findings, and provides a chemical vapor deposition raw material containing a metal compound represented by the following general formula (I) and a method for producing ceramics using the raw material. Is.
[Chemical 2]
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0011]
In the metal compound represented by the above general formula (I) according to the present invention, examples of the alkyl group having 1 to 8 carbon atoms represented by R include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tertiary Examples include butyl, isobutyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl and 2-ethylhexyl.
[0012]
Specific examples of the metal compound represented by the general formula (I) according to the present invention include, for example, Compound Nos. 1-4 are mentioned.
[0013]
[Chemical 3]
The metal compound represented by the general formula (I) according to the present invention is not particularly limited in its production method. As the production method, for example, chlorides of tetravalent metal elements (Chitaniu beam), nitrates, and inorganic salt or a hydrate thereof, such as sulfate, sodium hydroxide and trialkyl silanols appropriate structure, ammonia , A method of producing by reacting in the presence of a base such as an amine, reacting an inorganic salt of a tetravalent metal element or a hydrate thereof with a trialkylsilanol such as trialkylsilyloxy sodium and an alkali metal alkoxide compound. And a method of production by an exchange reaction between an alkoxide of a low-molecular alcohol such as tetramethoxide, tetraethoxide, tetraisopropoxide and tetrabutoxide of a tetravalent metal element and a trialkylsilanol.
[0015]
The chemical vapor deposition (CVD) raw material of the present invention contains the above-mentioned metal compound, and its form is appropriately selected depending on the method of transport and supply of the CVD method used. It is.
[0016]
As a transportation supply method, the CVD raw material is vaporized by heating and / or reducing the pressure in the raw material container, and introduced into the deposition reaction section together with a carrier gas such as argon, nitrogen, and helium used as necessary. There is a liquid transport method in which a CVD raw material is transported to a vaporization chamber in a liquid or solution state, vaporized by heating and / or decompressing in the vaporization chamber, and introduced into a deposition reaction section. In the case of the gas transport method, the above metal compound itself is a raw material for CVD. In the case of the liquid transport method, the metal compound itself or a metal compound solution obtained by dissolving the metal compound in an organic solvent is the raw material for CVD.
[0017]
In addition, in the multi-component CVD method for producing a multi-component thin film, a method of supplying CVD raw materials independently for each component (hereinafter sometimes referred to as a single source method) and a multi-component raw material are desired in advance. There is a method of supplying a mixed raw material mixed in the composition (hereinafter sometimes referred to as a cocktail sauce method). In the case of the cocktail source method, a mixture or a mixed solution of the metal compound according to the present invention and the metal source compound of other components is a raw material for CVD.
[0018]
The organic solvent used for the above-mentioned CVD raw material is not particularly limited, and a known general organic solvent can be used. Examples of the organic solvent include alcohols such as methanol, ethanol, 2-propanol and n-butanol; acetates such as ethyl acetate, butyl acetate and methoxyethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ether alcohols such as ethylene glycol monobutyl ether and diethylene glycol monomethyl ether; ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and dibutyl ether; methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone and dipropyl ketone , Diisobutyl ketone, methyl amyl ketone, cyclohexanone, methyl cyclohexa Ketones such as hexane; hydrocarbons such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane, toluene, xylene, etc., and these include solubility of solute, relationship between operating temperature and boiling point, flash point, etc. Is appropriately selected.
[0019]
As the metal source compound of the above other components, a compound that is not particularly limited and that becomes a well-known general CVD raw material can be used. Examples of the metal source compound include a compound of one or more organic coordination compounds such as an alcohol compound, a glycol compound, a β-diketone compound, and a cyclopentadiene compound and a metal.
[0020]
As the metal source compound of the other components, for example, when producing a silicate optical glass, the silicon compound may be monosilane, disilane, trimethylsilane, triethylsilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxy. Silane, tetraisopropoxysilane, tetrabutoxysilane, octamethylcyclotetrasiloxane, hexamethoxydisiloxane, hexaethoxydisiloxane, trimethoxymethylsilane, triethoxymethylsilane, trimethylmethoxysilane, trimethylethoxysilane, hexamethyldisiloxane, etc. Examples of the boron compound include borane, diborane, trimethyl borate, triethyl borate, trimethyl boron, and triethyl boron. Examples of the phosphorus compound include trimethyl. Examples include sulfate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite and the like. As the silicon-boron compound and silicon-phosphorus compound, Examples include tris (trimethylsilyl) borate and dimethyl (trimethylsilyl) phosphite described in JP-A-2-12916. Examples of aluminum compounds include trimethylaluminum, triethylaluminum, tributylaluminum, trimethoxyaluminum, triethoxyaluminum, Isopropoxyaluminum, tris (2,2,6,6-tetramethylheptane-3,5-dionato) aluminum, etc. Examples of the rare earth compound, lanthanum, praseodymium, erbium, and β- diketone complexes of thulium.
[0021]
The CVD raw material of the present invention may contain a nucleophilic reagent as needed to impart stability of the metal compound. Examples of the nucleophile include ethylene glycol ethers such as glyme, diglyme, triglyme and tetraglyme, 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, Crown ethers such as dibenzo-24-crown-8, ethylenediamine, N, N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7-penta Polyamines such as methyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, cyclic polyamines such as cyclam and cyclen, methyl acetoacetate, ethyl acetoacetate, acetoacetate-2-methoxye Β-ketoesters or β-diketones, such as ruthenium, are used, and the amount of these stabilizers used is in the range of 0.1 mol to 10 mol, preferably 1 to 4 mol, relative to 1 mol of the metal compound. Used in.
[0022]
The ceramic manufacturing method of the present invention is based on the chemical vapor deposition (CVD) method using the CVD raw material described above. The CVD method is a method in which a vaporized raw material and a reactive gas used as necessary are introduced onto a substrate, and then the raw material is decomposed and / or reacted on the substrate to grow and deposit ceramics on the substrate. Point to. The production method of the present invention is not particularly limited with respect to the raw material transport and supply method, the deposition method, the production conditions, the production apparatus, and the like, and well-known general conditions and methods can be used.
[0023]
Examples of the reactive gas used as necessary include oxygen, ozone, nitrogen dioxide, and nitric oxide.
[0024]
Examples of the transport and supply method include the gas transport method, the liquid transport method, the single source method, and the cocktail sauce method described above.
[0025]
In addition, the above deposition methods include thermal CVD in which raw material gas or raw material gas and reactive gas are reacted only by heat to deposit ceramics, plasma CVD using heat and plasma, photo CVD using heat and light, heat And photo-plasma CVD using light and plasma.
[0026]
Moreover, as said manufacturing conditions, reaction temperature (substrate temperature), reaction pressure, a deposition rate, etc. are mentioned. About reaction temperature, 200 degreeC or more which is the temperature which said metal compound based on this invention which is a raw material fully reacts is preferable, and 350-800 degreeC is more preferable. The reaction pressure is preferably from atmospheric pressure to 100 Pa in the case of thermal CVD and photo CVD, and is preferably from 100 to 2000 Pa in the case of using plasma. The deposition rate can be controlled by the raw material supply conditions (vaporization temperature, vaporization pressure), reaction temperature, and reaction pressure. When the deposition rate is large, the characteristics of the obtained ceramic may be deteriorated. When the deposition rate is small, a problem may occur in productivity efficiency, so 20 to 1000 nm / min is preferable, and 50 to 500 nm / min is more preferable.
[0027]
In the ceramic manufacturing method of the present invention, if step filling is necessary, a reflow process may be provided after ceramic layer deposition. In this case, the reflow temperature is 600 to 1200 ° C, preferably 700 to 1000 ° C.
[0028]
The CVD raw material of the present invention and the method for producing ceramics using the same are particularly preferably used for the production of silicate optical glass used for optical fibers, optical waveguides, optical amplifiers, optical switches, etc., which are members of optical communication systems. It is what is done. The silicate optical glass is oxidized to a silicate glass made of silicon oxide and optionally containing aluminum oxide, boron oxide, phosphorus oxide, oxides of rare earth elements (lanthanum, praseodymium, erbium, thulium, etc.). Examples thereof include those doped with one or more selected from titanium, germanium oxide, zirconium oxide, tin oxide, hafnium oxide, and lead oxide. Moreover, 0.1-25 are preferable with respect to the silicon element 100, and, as for the molar ratio of the metal element represented by M in these silicate type | system | group optical glass, 1-15 are more preferable.
[0029]
【Example】
Hereinafter, the present invention will be described in more detail with examples, comparative examples, and evaluation examples. However, the present invention is not limited in any way by the following examples, comparative examples and evaluation examples.
[0030]
[Example 1]
A test sample in which a 20 μm silicate optical glass layer was deposited on a 6-inch silicon wafer was manufactured by the CVD method according to the following method and conditions. The same applies to the following examples and comparative examples.
Raw material (temperature): Compound No. 1 (75 ° C)
Raw material transportation supply method: Gas transportation, Single source deposition method: Thermal CVD
Reactive gas: Ozone, oxygen Reaction pressure: 400-800Pa
Substrate temperature: 450 ° C
Deposition rate: 150 nm / min
[Example 2]
Raw material (temperature): Compound No. 1 (110 ° C), hexamethyldisiloxane (10 ° C)
Raw material transportation supply method: Gas transportation, Single source deposition method: Thermal CVD
Reactive gas: Ozone, oxygen Reaction pressure: Atmospheric pressure Substrate temperature: 450 ° C
Deposition rate: 170 nm / min
Example 3
Raw material (temperature): Compound No. 1 (100 ° C), tetraethoxysilane (55 ° C)
Raw material transportation supply method: Gas transportation, Single source deposition method: Thermal CVD
Reactive gas: Ozone, oxygen Reaction pressure: 800-1000Pa
Substrate temperature: 450 ° C
Deposition rate: 210 nm / min
Example 4
Raw material (temperature): Compound No. 1 (100 ° C), hexamethyldisiloxane (10 ° C)
Raw material transportation supply method: Gas transportation, Single source deposition method: Thermal CVD
Reactive gas: ozone, oxygen reaction pressure: 1000-1200 Pa
Substrate temperature: 450 ° C
Deposition rate: 220 nm / min
Example 5
Raw material (temperature): Compound No. 1 (75 ° C), tris (trimethylsilyl) borate (30 ° C)
Raw material transportation supply method: Gas transportation, Single source deposition method: Thermal CVD
Reactive gas: Ozone, oxygen Reaction pressure: 400-800Pa
Substrate temperature: 450 ° C
Deposition rate: 170 nm / min
[Comparative Example 1]
Raw material (temperature): tetraisopropoxy titanium (55 ° C), tetraethoxysilane (65 ° C)
Raw material transportation supply method: Gas transportation, Single source deposition method: Thermal CVD
Reactive gas: ozone, oxygen reaction pressure: 600-1000 Pa
Substrate temperature: 450 ° C
Deposition rate: 180 nm / min
[Evaluation example]
About the test sample obtained by said Example and comparative example, the element analysis by the energy dispersive X ray analysis method (EDX) was performed about the same location (4 places), respectively. Variation in composition was evaluated by comparing two locations (point A and point B) of the combination having the largest composition ratio deviation among the four locations. The variation was shown by the ratio of each detection element, where the number of moles of silicon was 100. The results are shown in Tables 1 and 2 .
[0041]
[Table 1]
[Table 2]
【The invention's effect】
The present invention can provide a CVD raw material capable of easily controlling composition and suppressing dopant localization in a CVD method, and a method for producing ceramics using the same.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001151553A JP4640745B2 (en) | 2001-05-21 | 2001-05-21 | Raw material for chemical vapor deposition and method for producing ceramics using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001151553A JP4640745B2 (en) | 2001-05-21 | 2001-05-21 | Raw material for chemical vapor deposition and method for producing ceramics using the same |
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| Publication Number | Publication Date |
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| JP4640745B2 true JP4640745B2 (en) | 2011-03-02 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04331739A (en) * | 1991-04-30 | 1992-11-19 | Fujikura Ltd | Production of base material of optical fiber |
| JPH0693102A (en) * | 1991-11-06 | 1994-04-05 | Kanegafuchi Chem Ind Co Ltd | Silicon-based hybrid material |
| JPH06283507A (en) * | 1993-03-26 | 1994-10-07 | Kawasaki Steel Corp | Manufacture of semiconductor device |
| JPH09133827A (en) * | 1995-11-09 | 1997-05-20 | Nec Corp | Production of optical waveguide |
| JP2000227525A (en) * | 1999-02-05 | 2000-08-15 | Nhk Spring Co Ltd | Film forming device for optical waveguide and film forming method for optical waveguide |
| WO2001025502A1 (en) * | 1999-10-07 | 2001-04-12 | Advanced Technology Materials, Inc. | COMPOSITION AND METHOD FOR CVD DEPOSITION OF Zr/Hf SILICATE FILMS |
| JP2002246388A (en) * | 2000-11-30 | 2002-08-30 | Chartered Semiconductor Mfg Ltd | Method of forming zirconium oxide and hafnium oxide for material having high dielectric constant |
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- 2001-05-21 JP JP2001151553A patent/JP4640745B2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04331739A (en) * | 1991-04-30 | 1992-11-19 | Fujikura Ltd | Production of base material of optical fiber |
| JPH0693102A (en) * | 1991-11-06 | 1994-04-05 | Kanegafuchi Chem Ind Co Ltd | Silicon-based hybrid material |
| JPH06283507A (en) * | 1993-03-26 | 1994-10-07 | Kawasaki Steel Corp | Manufacture of semiconductor device |
| JPH09133827A (en) * | 1995-11-09 | 1997-05-20 | Nec Corp | Production of optical waveguide |
| JP2000227525A (en) * | 1999-02-05 | 2000-08-15 | Nhk Spring Co Ltd | Film forming device for optical waveguide and film forming method for optical waveguide |
| WO2001025502A1 (en) * | 1999-10-07 | 2001-04-12 | Advanced Technology Materials, Inc. | COMPOSITION AND METHOD FOR CVD DEPOSITION OF Zr/Hf SILICATE FILMS |
| JP2002246388A (en) * | 2000-11-30 | 2002-08-30 | Chartered Semiconductor Mfg Ltd | Method of forming zirconium oxide and hafnium oxide for material having high dielectric constant |
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