CN1821251A - 用于二氧化硅或金属硅酸盐薄膜的前体 - Google Patents
用于二氧化硅或金属硅酸盐薄膜的前体 Download PDFInfo
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- CN1821251A CN1821251A CNA2005101373594A CN200510137359A CN1821251A CN 1821251 A CN1821251 A CN 1821251A CN A2005101373594 A CNA2005101373594 A CN A2005101373594A CN 200510137359 A CN200510137359 A CN 200510137359A CN 1821251 A CN1821251 A CN 1821251A
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- 239000002243 precursor Substances 0.000 title description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title description 6
- 229910052914 metal silicate Inorganic materials 0.000 title description 4
- 239000000377 silicon dioxide Substances 0.000 title description 3
- -1 metalloid silicate Chemical class 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229910052752 metalloid Inorganic materials 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 31
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 31
- JYVBNFXXWVYHSW-UHFFFAOYSA-N hydroxy(propan-2-yloxy)silane Chemical class C(C)(C)O[SiH2]O JYVBNFXXWVYHSW-UHFFFAOYSA-N 0.000 claims description 25
- 125000003545 alkoxy group Chemical group 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- 150000004819 silanols Chemical class 0.000 claims description 13
- 150000002737 metalloid compounds Chemical class 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 9
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- OZWCXTBBBIAOAT-UHFFFAOYSA-N chloromethane silane Chemical compound [SiH4].ClC OZWCXTBBBIAOAT-UHFFFAOYSA-N 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 150000002738 metalloids Chemical class 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims 1
- 229910052987 metal hydride Inorganic materials 0.000 claims 1
- 150000004681 metal hydrides Chemical class 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000005049 silicon tetrachloride Substances 0.000 claims 1
- NXEPWVPWSWRGLP-UHFFFAOYSA-N hydroxy-(2-methylbutan-2-yloxy)-bis[(2-methylpropan-2-yl)oxy]silane Chemical compound CCC(C)(C)O[Si](O)(OC(C)(C)C)OC(C)(C)C NXEPWVPWSWRGLP-UHFFFAOYSA-N 0.000 abstract 1
- XUZMGPPDEWMALW-UHFFFAOYSA-N hydroxy-(2-methylbutan-2-yloxy)-di(propan-2-yloxy)silane Chemical compound CCC(C)(C)O[Si](O)(OC(C)C)OC(C)C XUZMGPPDEWMALW-UHFFFAOYSA-N 0.000 abstract 1
- FNVCPESKXNYSRN-UHFFFAOYSA-N hydroxy-[(2-methylpropan-2-yl)oxy]-di(propan-2-yloxy)silane Chemical compound CC(C)O[Si](O)(OC(C)C)OC(C)(C)C FNVCPESKXNYSRN-UHFFFAOYSA-N 0.000 abstract 1
- DIVDDOMEZHCODA-UHFFFAOYSA-N hydroxy-bis(2-methylbutan-2-yloxy)-[(2-methylpropan-2-yl)oxy]silane Chemical compound CCC(C)(C)O[Si](O)(OC(C)(C)C)OC(C)(C)CC DIVDDOMEZHCODA-UHFFFAOYSA-N 0.000 abstract 1
- OFFJSCPPFVVFAJ-UHFFFAOYSA-N hydroxy-bis(2-methylbutan-2-yloxy)-propan-2-yloxysilane Chemical compound CCC(C)(C)O[Si](O)(OC(C)C)OC(C)(C)CC OFFJSCPPFVVFAJ-UHFFFAOYSA-N 0.000 abstract 1
- MBMITMZVBNZJTQ-UHFFFAOYSA-N hydroxy-bis[(2-methylpropan-2-yl)oxy]-propan-2-yloxysilane Chemical compound CC(C)O[Si](O)(OC(C)(C)C)OC(C)(C)C MBMITMZVBNZJTQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000002002 slurry Substances 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910003902 SiCl 4 Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005304 joining Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- NCCPPOZTBYQIPS-UHFFFAOYSA-N butoxy(hydroxy)silane Chemical compound CCCCO[SiH2]O NCCPPOZTBYQIPS-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MBCITRBMMWOBGO-UHFFFAOYSA-N dichloro(propan-2-yloxy)silane Chemical compound C(C)(C)O[SiH](Cl)Cl MBCITRBMMWOBGO-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/04—Esters of silicic acids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/22—Magnesium silicates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Silicon Polymers (AREA)
- Glass Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
一种选自双(叔丁氧基)(异丙氧基)甲硅烷醇、双(异丙氧基)(叔丁氧基)甲硅烷醇、双(叔戊氧基)(异丙氧基)甲硅烷醇、双(异丙氧基)(叔戊氧基)甲硅烷醇、双(叔戊氧基)(叔丁氧基)甲硅烷醇、双(叔丁氧基)(叔戊氧基)甲硅烷醇及其混合物的组合物；其在基底上形成金属或准金属硅酸盐层的应用以及混合烷氧基甲硅烷醇的合成。
Description
发明背景
烷氧基甲硅烷醇在电子器件的制造中正日益受到关注，其中它们与含金属的前体反应而沉积含硅和金属材料的薄膜。特别的，随着元件器件(如晶体管)尺寸减小以及元件器件和电路图案密度增加，那些元件器件和电路之间的传统的二氧化硅介电绝缘材料已不适用，工业界已在探求能在相对较低的温度下沉积的更好的介电材料。已经研究了在低于300℃的温度下与含金属的化合物反应的烷氧基甲硅烷醇，以获得电绝缘较小电子元件器件和电路所需的低介电绝缘材料，这些电子元件器件和电路具有增加的密度和较小的整体尺寸。
WO 02/27063公开了用于与含金属或准金属的前体反应以沉积金属或准金属硅酸盐的烷氧基甲硅烷醇，例如三(叔丁氧基)甲硅烷醇。烷氧基甲硅烷醇通常被描述为含有：[(R1)(R2)(R3)CO]-[(R4(R5)(R6)CO]-[(R7)(R8)(R9)CO]-SiOH；其中Rn可以相同或不同，n＝1-9。
WO 03/083167也公开了与WO 02/270063公开的相同范围的用于与含铝的前体反应而生成硅铝酸盐的烷氧基甲硅烷醇。
Backer等在“Esters Mixtes De L’Acide Tetrathio-Orthosilicique”，Rec.Trav.Chim.，61(1942)，pp500-512中公开了三(丁氧基)甲硅烷醇的合成。
Goedel等在“Hyperbranched Poly(alkoxysilonanes)”，Polymer Preprints，42(1)，(2001)，pp 242-243中公开了烷氧基甲硅烷醇如三(乙氧基)甲硅烷醇的聚合。
Hausman等在“Rapid Vapor Deposition of Highly Conformal SilicaNanoaluminates”，Science，Vol.298，10/11/2002，pp 402-406中公开了三(叔丁氧基)甲硅烷醇和三甲基铝按交替顺序以原子层沉积(ALD)形成薄膜，该薄膜可用于电子应用。
Muller，Richard在“Zur Darstellung von Alkoxy-und Alkoxysiloxy-silanolen”，Z.Chem.，23，Jg.(1983)，p252，表1最后一条和表2中确定了各种三(烷氧基)甲硅烷醇，后者中包括三(苯氧基)甲硅烷醇。
Schott等在“Alkoxy-silanole-partielle Kieselsaureester”，Z.Anorg.Allg.Chemie，459，(1979)，pp 177-186中公开了三烷氧基甲硅烷醇和二烷氧基甲硅烷二醇的合成。
目前所关注的用于制备二氧化硅-金属薄膜的烷氧基甲硅烷醇因不需要的物理性质而受到妨碍。为便于应用，烷氧基甲硅烷醇应当易于合成，能够获得高纯度并且易于从存放地运送到反应地。本发明的新烷氧基甲硅烷醇克服了现有技术的不足，在制备二氧化硅-金属薄膜上表现出以下将要证明的优良性能。
发明概述
本发明是选自双(叔丁氧基)(异丙氧基)甲硅烷醇、双(异丙氧基)(叔丁氧基)甲硅烷醇、双(叔戊氧基)(异丙氧基)甲硅烷醇、双(异丙氧基)(叔戊氧基)甲硅烷醇、双(叔戊氧基)(叔丁氧基)甲硅烷醇、双(叔丁氧基)(叔戊氧基)甲硅烷醇及其混合物的组合物；该组合物在基底上形成金属或准金属硅酸盐层的应用以及该混合烷氧基甲硅烷醇的合成。
附图简述
附图是现有技术烷氧基甲硅烷醇；三(叔戊氧基)甲硅烷醇(TPOSL)与本发明新的混合烷氧基甲硅烷醇；双(叔丁氧基)(异丙氧基)甲硅烷醇(BTBIPOSL)的蒸气压比较图，图中显示双(叔丁氧基)(异丙氧基)甲硅烷醇在使用烷氧基甲硅烷醇的薄膜沉积过程的优选可能的操作温度范围中表现出一致的高出10倍的蒸气压。
发明详述
本发明涉及一类新的混合烷氧基甲硅烷醇，其合成及应用。此混合烷氧基甲硅烷醇可用作在低于500℃温度下通过化学气相沉积(CVD)或原子层沉积(ALD)制备硅或金属硅酸盐的潜在前体。这些化合物按如下制备：将SiCl4与两当量的大体积醇(HOR1)，如叔丁醇或叔戊醇，在碱存在下反应或者与金属醇盐((MOR1，即醇的金属盐)反应，随后加入一当量的较小体积的醇(HOR2)，如异丙醇，在碱存在下或者加入相应的金属醇盐(MOR2)，然后低温水解。
混合烷氧基甲硅烷醇在室温下是液态并且是热稳定的。由于TBOSL室温下为固体而TPOSL的蒸气压非常低(96℃时约为2托)，作为液体并且具有较高蒸气压的这些新混合物是比那些市售三(烷氧基)甲硅烷醇，如三(叔丁氧基)甲硅烷醇(TBOSL)或三(叔戊氧基)甲硅烷醇(TPOSL)更好的前体。
这些新的、热稳定的混合烷氧基甲硅烷醇已被制备作为形成低热预算的(budged)金属硅酸盐或二氧化硅薄膜的潜在前体。在混合烷氧基甲硅烷醇当中，双(叔丁氧基)(异丙氧基)甲硅烷醇易于制备并且能以半导体工业所要求的高纯度生产。双(叔丁氧基)(异丙氧基)甲硅烷醇的蒸气压比半导体工业目前评价为ALD SiO2潜在来源的前体三(叔戊氧基)甲硅烷醇(TPOSL)高约10倍(见附图)，这使得该混合烷氧基甲硅烷醇成为CVD或ALD前体中更好的前体。
三(烷氧基)甲硅烷醇前体可商购得到。其可通过两步法制备，即以反应式1或反应式2反应，然后按反应式3水解。
混合烷氧基甲硅烷醇的合成更为复杂，包含如反应式4至7所示的三步过程。
其中，n＝1-2；m＝1-2且n+m＝3。
为生成稳定的混合烷氧基甲硅烷醇，在第一步(反应式4或5)中优先选择大体积的醇以阻止氯配位体的进一步取代，使得SiCl4定量转化为单烷氧基三氯甲硅烷或双(烷氧基)二氯甲硅烷。如果烷氧基基团不够庞大，将会生成烷氧基三氯甲硅烷、双(烷氧基)二氯甲硅烷和三(烷氧基)氯甲硅烷的混合物。因此，第一步中优选叔丁醇或叔戊醇。优选，用两当量的大体积醇来生成双(烷氧基)二氯甲硅烷。第二步中不同醇的体积也应当足够大，以防止生成完全取代的烷氧基甲硅烷，但是为避免甲硅烷醇的完全取代只需要一当量的第二种醇。
例如，如果在第一步中用两当量叔丁醇并在第二步中用两当量的异丙醇，就会生成不希望的双(叔丁氧基)双(异丙氧基)甲硅烷。由于它们的沸点一般非常接近，因而很难将所得完全取代的烷氧基甲硅烷从最终产物混合烷氧基甲硅烷醇中除去。
副产物HCl对生成的混合烷氧基甲硅烷醇的稳定性有影响。有两种去除反应产生的HCl的方法：作为有机碱盐，如盐酸吡啶；或者作为无机碱。鉴于有机碱在随后的分离或CVD/ALD方法中可能引起问题，无机碱优于有机碱。反应温度对于混合烷氧基甲硅烷醇的成功合成也很重要，因为较高的温度促进其它反应，这导致生成后来难以用蒸馏分离出去的产物。
下面的实施例证明能够获得所需的混合烷氧基甲硅烷醇。实际大规模生产这些混合物的过程可取决于混合物本身而改变。
实施例1.合成双(异丙氧基)(叔戊氧基)甲硅烷醇
将20g(0.118mol)SiCl4加入装有500ml己烷的1000ml三颈烧瓶中。用装有干冰和异丙醇的冷浴将烧瓶冷却到-40℃。通过滴加漏斗缓慢加入18ml(0.237mol)异丙醇和11.3ml(0.118mol)叔戊醇。保持温度低于-20℃。向烧瓶中缓慢加入30ml吡啶，产生大量白色盐酸吡啶沉淀。移去冷浴，将烧瓶搅拌3小时。反应混合物的气相色谱/质谱(GC/MS)测定显示生成了双(异丙氧基)(叔戊氧基)氯甲硅烷，外加其他产物。过滤并除去溶剂后得到约23g白色浆液。将白色浆液在低于-20℃温度下逐滴加入到含有40ml乙醚、15ml水和15ml吡啶的溶液中，直至滴加完毕。将生成的白色浆液搅拌3小时。分离有机层并用无水CaCl2干燥两天。GC/MS显示生成了主要产物双(异丙氧基)(叔戊氧基)甲硅烷醇(79.5％)，外加四-(异丙氧基)甲硅烷(2.8％)、三(异丙氧基)(叔戊氧基)甲硅烷(12.4％)和三(异丙氧基)甲硅烷醇(1.3％)。很难通过真空蒸馏将双(异丙氧基)(叔戊氧基)甲硅烷醇与三(异丙氧基)(叔戊氧基)甲硅烷分离。但是如果大规模合成，提纯产物还是可行的。
实施例2.合成双(异丙氧基)(叔丁氧基)甲硅烷醇
将20g(0.118mol)SiCl4加入装有500ml己烷的1000ml三颈烧瓶中。用装有干冰和异丙醇的冷浴将烧瓶冷却到-40℃。通过滴加漏斗缓慢加入11.3ml(0.118mol)叔丁醇。保持温度低于-20℃。向烧瓶中缓慢加入10ml吡啶，以产生大量白色盐酸吡啶沉淀。移去冷浴，将烧瓶搅拌3小时。向生成的白色浆液中缓慢加入18ml异丙醇和20ml吡啶的混合物。将反应混合物搅拌过夜。反应混合物的GC/MS测定显示生成了双(异丙氧基)(叔丁氧基)氯甲硅烷和三(异丙氧基)(叔丁氧基)甲硅烷。过滤并除去溶剂，得到白色浆液。将白色浆液在低于-20℃温度下逐滴加入到含有50ml乙醚、50ml水和15ml吡啶的溶液中，直至滴加完毕。将生成的白色浆液搅拌2小时。分离有机层并用无水CaCl2干燥两天。GC/MS显示生成了主要产物双(异丙氧基)(叔丁氧基)甲硅烷醇(55％)，外加三(异丙氧基)(叔丁氧基)甲硅烷(34％)。
实施例3.合成双(叔丁氧基)(异丙氧基)甲硅烷醇
将20g(0.118mol)SiCl4加入装有400ml己烷的1000ml三颈烧瓶中。用装有干冰和异丙醇的冷浴将烧瓶冷却到-40℃。通过滴加漏斗缓慢加入22.6ml(0.236mol)叔丁醇。保持温度低于-20℃。向烧瓶中缓慢加入20ml吡啶，产生大量白色盐酸吡啶沉淀。移去冷浴，将烧瓶在移去冷浴后搅拌过夜。过滤后在低于40℃下向滤液中加入9ml(0.118mol)的异丙醇。向生成的白色浆液中缓慢加入10ml吡啶。反应混合物在移去冷浴后搅拌5小时。过滤并除去溶剂后得到白色浆液。将白色浆液在低于-0℃温度下逐滴加入到含有50ml乙醚、50ml水和15ml吡啶的溶液中，直至滴加完毕。将生成的白色浆液搅拌过夜。分离有机层并用无水CaCl2干燥几日。GC/MS显示生成了主要产物双(叔丁氧基)(异丙氧基)甲硅烷醇(＞80％)，外加双(异丙氧基)-双(叔丁氧基)甲硅烷。真空蒸馏得到纯双(叔丁氧基)(异丙氧基)甲硅烷醇(～104℃/2托)。热解分析/微分扫描热量测定(TGA/DSC)显示其沸点为207℃。
实施例4.合成双(叔丁氧基)(异丙氧基)甲硅烷醇
将由SiCl4和两当量叔丁醇在吡啶存在下反应生成的20g(0.0799mol)双(叔丁氧基)二氯甲硅烷加入装有200ml己烷的1000ml三颈烧瓶中。用装有干冰和异丙醇的冷浴将烧瓶冷却到-20℃。加入4.8g(0.08mol)异丙醇。保持温度低于-20℃。向烧瓶中缓慢加入6.3g吡啶，产生大量白色盐酸吡啶沉淀。移去冷浴，将烧瓶在移去冷浴后于室温下搅拌几日。过滤并除去溶剂，得到白色浆液。将白色浆液在低于-10℃温度下逐滴加入到含有50ml乙醚、50ml水和6gNH4·HCO3的溶液中，直至滴加完毕。将生成的白色浆液搅拌过夜。分离有机层并用无水CaCl2干燥。GC/MS显示生成了主产物双(叔丁氧基)(异丙氧基)甲硅烷醇(93.8％)，外加双(叔丁氧基)(异丙氧基)二氯甲硅烷。真空蒸馏得到纯双(叔丁氧基)(异丙氧基)甲硅烷醇(～104℃/2托)。
由于TBOSL室温下为固体而TPOSL的蒸气压非常低(96℃约为2托)，作为液体并且具备较高的蒸气压的这些新的混合烷氧基甲硅烷醇是比那些市售三(烷氧基)甲硅烷醇，如三(叔丁氧基)甲硅烷醇(TBOSL)或三(叔戊氧基)甲硅烷醇(TPOSL)更好的前体。
本发明新的混合烷氧基甲硅烷醇可有利地用于在基底上形成金属或准金属硅酸盐的方法中，如固态晶体管、电容器、微通路和电路的电子器件制造中的介电层，一般通过使含金属或准金属的化合物与选自双(叔丁氧基)(异丙氧基)甲硅烷醇、双(异丙氧基)(叔丁氧基)甲硅烷醇、双(叔戊氧基)(异丙氧基)甲硅烷醇、双(异丙氧基)(叔戊氧基)甲硅烷醇、双(叔戊氧基)(叔丁氧基)甲硅烷醇、双(叔丁氧基)(叔戊氧基)甲硅烷醇及其混合物的混合烷氧基甲硅烷醇接触，并使含金属或准金属的化合物与混合烷氧基甲硅烷醇反应而在基底上形成金属或准金属硅酸盐。优选地，混合烷氧基甲硅烷醇和含金属或准金属的化合物各自为液态，以易于将其运送到在其中二者混合并反应的反应室或设备中，并且它们都优选在低温下在反应室或设备中蒸发以维持所制电子器件的热平衡。典型地，金属或准金属选自钛、铪、锆、钇、镧、钪、镁、硼、铝及其混合物。用于制备金属或准金属化合物的配体可以是酰胺、烷基化物、醇盐、卤化物及其混合物。
本发明描述了几个优选的实施方式，但是本发明的全部范围应当由下述权利要求确定。
Claims (17)
1、一种组合物，该组合物选自双(叔丁氧基)(异丙氧基)甲硅烷醇、双(异丙氧基)(叔丁氧基)甲硅烷醇、双(叔戊氧基)(异丙氧基)甲硅烷醇、双(异丙氧基)(叔戊氧基)甲硅烷醇、双(叔戊氧基)(叔丁氧基)甲硅烷醇、双(叔丁氧基)(叔戊氧基)甲硅烷醇及其混合物。
2、权利要求1的组合物，其中组合物是双(异丙氧基)(叔丁氧基)甲硅烷醇。
3、权利要求1的组合物，其中组合物是双(叔戊氧基)(异丙氧基)甲硅烷醇。
4.权利要求1的组合物，其中组合物是双(异丙氧基)(叔戊氧基)甲硅烷醇。
5、权利要求1的组合物，其中组合物是双(叔戊氧基)(叔丁氧基)甲硅烷醇。
6、权利要求1的组合物，其中组合物是双(叔丁氧基)(叔戊氧基)甲硅烷醇。
7、双(叔丁氧基)(异丙氧基)甲硅烷醇。
8、一种在基底上形成金属或准金属硅酸盐的方法，包括：
使含金属或准金属的化合物与选自双(叔丁氧基)(异丙氧基)甲硅烷醇、双(异丙氧基)(叔丁氧基)甲硅烷醇、双(叔戊氧基)(异丙氧基)甲硅烷醇、双(异丙氧基)(叔戊氧基)甲硅烷醇、双(叔戊氧基)(叔丁氧基)甲硅烷醇、双(叔丁氧基)(叔戊氧基)甲硅烷醇及其混合物的混合烷氧基甲硅烷醇接触，并使含金属或准金属的化合物与所述混合烷氧基甲硅烷醇反应而在基底上形成金属或准金属硅酸盐。
9、权利要求8的方法，其中含金属或准金属的化合物在反应中为气态。
10、权利要求8的方法，其中混合烷氧基甲硅烷醇在反应中为气态。
11、权利要求8的方法，其中混合烷氧基甲硅烷醇是双(叔丁氧基)(异丙氧基)甲硅烷醇。
12、权利要求8的方法，其中金属或准金属选自钛、铪、锆、钇、镧、钪、镁、硼、铝及其混合物。
13、权利要求12的方法，其中含金属或准金属的化合物选自金属氨基化物、金属醇盐、金属氢化物、烷基金属及其混合物。
14、一种在基底上形成金属或准金属硅酸盐的方法，包括；
使含金属或准金属的化合物与双(叔丁氧基)(异丙氧基)甲硅烷醇接触，并使含金属或准金属的化合物与双(叔丁氧基)(异丙氧基)甲硅烷醇反应而在基底上形成金属或准金属硅酸盐。
15、一种合成混合烷氧基甲硅烷醇的方法，包括；
使四氯化硅与第一烷醇或其金属盐反应生成烷氧基氯甲硅烷，并进一步使烷氧基氯甲硅烷与第二烷醇或其金属盐反应生成混合烷氧基甲硅烷醇，其中第一烷醇与第二烷醇不同。
16、权利要求14的方法，其中第一烷醇为叔丁醇，第二烷醇为异丙醇。
17、权利要求14的方法，其中第一烷醇为叔戊醇，第二烷醇为异丙醇。
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| US2995593A (en) * | 1958-06-30 | 1961-08-08 | California Research Corp | Hexaalkoxydisiloxanes |
| US6969539B2 (en) | 2000-09-28 | 2005-11-29 | President And Fellows Of Harvard College | Vapor deposition of metal oxides, silicates and phosphates, and silicon dioxide |
| JP4959921B2 (ja) | 2002-03-28 | 2012-06-27 | プレジデント アンド フェロウズ オブ ハーバード カレッジ | 二酸化珪素ナノラミネートの蒸着 |
-
2004
- 2004-12-09 US US11/008,069 patent/US7064227B1/en active Active
-
2005
- 2005-12-06 DE DE602005006948T patent/DE602005006948D1/de not_active Expired - Fee Related
- 2005-12-06 EP EP05026611A patent/EP1669361B1/en not_active Not-in-force
- 2005-12-06 TW TW094143055A patent/TW200624438A/zh unknown
- 2005-12-06 AT AT05026611T patent/ATE396193T1/de not_active IP Right Cessation
- 2005-12-08 KR KR1020050119363A patent/KR100651993B1/ko not_active IP Right Cessation
- 2005-12-09 JP JP2005355620A patent/JP2006160744A/ja not_active Withdrawn
- 2005-12-09 CN CNA2005101373594A patent/CN1821251A/zh active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686773A (zh) * | 2010-03-16 | 2012-09-19 | 东京毅力科创株式会社 | 成膜方法和成膜装置 |
| US8765221B2 (en) | 2010-03-16 | 2014-07-01 | Tokyo Electron Limited | Film forming method and film forming apparatus |
| CN116284096A (zh) * | 2023-05-19 | 2023-06-23 | 研峰科技(北京)有限公司 | 一种超低氯离子含量的三(叔丁氧基)硅烷醇的合成方法 |
| CN116284096B (zh) * | 2023-05-19 | 2023-09-19 | 研峰科技(北京)有限公司 | 一种超低氯离子含量的三(叔丁氧基)硅烷醇的合成方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100651993B1 (ko) | 2006-12-01 |
| EP1669361A1 (en) | 2006-06-14 |
| JP2006160744A (ja) | 2006-06-22 |
| DE602005006948D1 (de) | 2008-07-03 |
| EP1669361B1 (en) | 2008-05-21 |
| KR20060065519A (ko) | 2006-06-14 |
| US7064227B1 (en) | 2006-06-20 |
| US20060127578A1 (en) | 2006-06-15 |
| TW200624438A (en) | 2006-07-16 |
| ATE396193T1 (de) | 2008-06-15 |
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