CN104341447A - Compound containing N amidino-silicon and application thereof - Google Patents
Compound containing N amidino-silicon and application thereof Download PDFInfo
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- CN104341447A CN104341447A CN201410621520.4A CN201410621520A CN104341447A CN 104341447 A CN104341447 A CN 104341447A CN 201410621520 A CN201410621520 A CN 201410621520A CN 104341447 A CN104341447 A CN 104341447A
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- Prior art keywords
- silicon
- alkyl
- cycloalkyl
- alkenyl
- aryl
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- 150000001875 compounds Chemical class 0.000 title abstract description 7
- SPJCSWPGRGOQNZ-UHFFFAOYSA-N C(N)(=N)[Si] Chemical compound C(N)(=N)[Si] SPJCSWPGRGOQNZ-UHFFFAOYSA-N 0.000 title abstract 2
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 41
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000011541 reaction mixture Substances 0.000 claims abstract description 23
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims abstract description 10
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 amido lithium Chemical compound 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 55
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 41
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 40
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 31
- 239000010408 film Substances 0.000 claims description 29
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 20
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000005229 chemical vapour deposition Methods 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000001272 nitrous oxide Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001409 amidines Chemical class 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 2
- 150000003927 aminopyridines Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 7
- 230000002708 enhancing effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 230000007812 deficiency Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 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 description 1
- DIVFUUKNPLVLKM-UHFFFAOYSA-N BCN[Si](C(C)(C1N=C=C)C2CCCCC2)(NC[U])(NC(C)(C)C)[NH+]1C1CCCCC1 Chemical compound BCN[Si](C(C)(C1N=C=C)C2CCCCC2)(NC[U])(NC(C)(C)C)[NH+]1C1CCCCC1 DIVFUUKNPLVLKM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- DVHMVRMYGHTALQ-UHFFFAOYSA-N silylhydrazine Chemical compound NN[SiH3] DVHMVRMYGHTALQ-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Abstract
The invention relates to a compound containing N amidino-silicon. The compound is prepared according to the following methods: (1) dissolving carbodiimide or derivatives thereof into a reaction solvent, adding an alkyl/amido lithium solution, aminopyridine or derivatives thereof and alkyl/amido lithium under the stirring condition of -78 DEG C to 0 DEG C according to the molar ratio of 1 to (1-1.2), restoring to room temperature, and then further stirring and reacting for 0.5-3 hours to obtain a reaction mixture; (2) filtering the reaction mixture obtained in the step (1) to obtain lithium salt solid, and dissolving the lithium salt solid into an organic solvent to obtain a lithium salt solution; (3) dropwise adding a silicon-containing reactant or a solution thereof to the lithium salt solution at -78 DEG C to 0 DEG C according to the molar ratio of lithium salt to silicon-containing reactant being (1-4) to (1-1.1), rising to a certain temperature and reacting for 3-10 hours; (4) filtering the reaction mixture obtained in the step (3), concentrating and crystallizing filtrate, or distilling at reduced pressure to obtain a silicon compound containing an amidine ligand. The compound disclosed by the invention can be applied to production of integrated circuits to prepare films of silicon nitride, carbon-containing silicon nitride and the like.
Description
Technical field
The present invention relates to one and have ad hoc structure namely containing N amidino groups silicon compound, this compounds can be used as integrated circuit thin-film material proplastid simultaneously, belongs to technical field of microelectronic material.
Background technology
Along with the development that IC industry is quick and optimum, also had with the requirement of its relevant industries that high technology content, high-quality require, the industry characteristic of three high requests of high entry threshold thereupon, namely this be face new challenges and opportunity for whole unicircuit associated materials.
In the numerous process procedure of unicircuit, silicon-containing film can be used as capacitor films, gate pole film, stops not, the optical component of the optical communication equipment such as the electronic component of the electronic unit such as gate insulation film or optical waveguides, photoswitch, image intensifer, have indispensable status in fields such as photoelectric materials, the development therefore for the silicon-containing film proplastid material of integrated circuit fields has very important practical significance and value.
In CVD/ALD Technology, the character of proplastid is most important, it require proplastid have suitable thermostability and higher volatile while, preparation also should be had simple, and easily the feature such as transport and storage is beneficial to produce and use.Current silicon-containing film proplastid material is gradually from traditional material, such as silane, silicon tetrachloride, disilicone hexachloride, dimethyldichlorosilane(DMCS), dichlorosilane etc. are to the silicoorganic compound transition with ad hoc structure group, and major cause has 3 points: 1) traditional proplastid material is mostly gas or highly volatile liquid not easily stores and transports; 2) traditional proplastid material has suitable toxicity, simultaneously because the chemical property that the extreme of self is active easily causes danger, needs to have high input fund for security work; 3) the general content of halogen of traditional proplastid material is high, in film-forming process, easily produce too much hydrogenchloride, can produce corrosion to equipment.These reasons hinder the industrialization development of traditional silicon-containing film proplastid material to a great extent, simultaneously along with the develop rapidly of IC industry, be badly in need of the novel material of one or more to make up the deficiency of traditional material, and then alternative traditional material, realize industrialization.So investigators start sight to turn to the silicoorganic compound with ad hoc structure group one after another.
Patent CN101648964A and CN102282291A discloses aminosilane proplastid, CN1518076A discloses diazanyl silane proplastid, this two classes proplastid to some extent solves the problem of the highly volatile of traditional material, and convenient storage, but owing to self containing more si-h bond, character is active, therefore still there are some potential danger and has certain toxicity.It is the aminosilane proplastid of basic boom that patent US2010/0285663A1 mainly describes with disilicone hexachloride, this type of proplastid toxicity is little and activity is moderate, but due to the existence of Si prediction skeleton, make its volatility relatively low to a certain extent on the contrary, be unfavorable for the further film forming application of presoma, the relative complex of this type of material synthesis simultaneously.As can be seen here, in patent disclosed in, although the proplastid of the silicon-containing film material found at present all to some extent solves the deficiency that traditional proplastid material exists, but possess suitable thermostability, activity and relative nontoxic and easily the proplastid material of synthesis is still very necessary simultaneously, and there is considerable actual application value.
Summary of the invention
The object of the invention is to overcome traditional silicon-containing film material proplastid and the deficiencies in the prior art, there is provided a kind of new type integrated circuit thin-film material with containing N amidino groups silicon compound proplastid, good solvability is had in the organic solvents such as normal hexane, toluene, ether, methylene dichloride, tetrahydrofuran (THF), there are good volatility and thermostability, toxicity is little, activity is moderate, and convenient storage and transport, have good film forming properties.
According to technical scheme provided by the invention, described in have logical formula I containing N amidino groups silicon compound proplastid:
Wherein R
1be selected from C
1~ C
10alkyl (as methyl, ethyl, n-propyl, sec.-propyl etc.), C
2~ C
10alkenyl (as vinyl, allyl group etc.), C
2~ C
10alkynyl group (as ethynyl, propargyl etc.), C
3~ C
10cycloalkyl (as cyclopropyl, cyclopentyl, cyclohexyl etc.), C
6~ C
17aryl (as phenyl, o-tolyl, naphthyl etc.) ,-N (SiMe
3)
2or-N (R
5r
6), wherein R
2, R
3independently be selected from C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl, wherein R
4, R
5, R
6independently be selected from hydrogen atom, halogen atom (F, Cl, Br, I), C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl ,-Si (R
2r
3r
4),
or-N (R
7r
8), wherein R
5, R
6independently be selected from hydrogen atom, C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl, wherein R
7, R
8independently be selected from hydrogen atom, C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl, wherein R
7, R
8it is asynchronously hydrogen atom.
The prepared preparation method containing N amidino groups silicon compound that can be used as integrated circuit thin-film material proplastid, is characterized in that, comprise the following steps:
(1) carbodiimide or derivatives thereof is dissolved in reaction solvent, the mass ratio of carbodiimide or derivatives thereof and reaction solvent is 1:10 ~ 1:20, alkane/amido lithium solution is added under keeping at-78 ~ 0 DEG C the condition stirred, the mol ratio of carbodiimide or derivatives thereof and lithium alkylide alkane/amine is 1:1 ~ 1.2, the concentration of alkane/amido lithium solution is 1.0 ~ 2.5M, and stirring velocity is 800 ~ 2000 revs/min; Continue stirring reaction after returning to room temperature 0.5 ~ 3 hour, obtain reaction mixture, described reaction solvent is normal hexane, toluene, methylene dichloride, tetrahydrofuran (THF) or ether;
(2) reaction mixture step (1) obtained filters, collect filter cake, obtain lithium salts solid, lithium salts solid is mixed with organic solvent, the mass ratio of lithium salts solid and organic solvent is 1:10 ~ 20, obtain lithium salt solution, described reaction solvent is normal hexane, toluene, methylene dichloride, tetrahydrofuran (THF) or ether;
(3) at-78 ~ 0 DEG C according to lithium salts and siliceous reactant molar ratio 1 ~ 4:1, siliceous reactant or its above-mentioned solution is dripped in above-mentioned lithium salt solution, slowly rise to certain temperature, described temperature is the reflux temperature of room temperature to solvent for use, continues stirring reaction 3 ~ 10 hours at this temperature;
(4) reaction mixture that step (3) obtains is filtered, filter vacuum concentrate rear low temperature crystallization or underpressure distillation obtain logical formula I containing N amidino groups silicon compound;
(5) or in step (3) stirring after 3 ~ 10 hours, at-78 ~ 0 DEG C, add the organic amine of 1 ~ 10 molar equivalent, slowly rise to certain temperature, described temperature is the reflux temperature of room temperature to solvent for use, continue stirring reaction at this temperature again 3 ~ 10 hours, filter vacuum concentrate rear low temperature crystallization or underpressure distillation obtain logical formula I containing N amidino groups silicon compound.
Further, above-mentionedly all to carry out under rare gas element is as the protection such as nitrogen, argon gas in steps.
Further, alkane described in step (1)/amido lithium solution is for having structure R
1the ether of Li or hexane solution, wherein R
1be selected from C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl ,-N (SiMe
3)
2or-N (R
5r
6), wherein R
5, R
6independently be selected from hydrogen atom, C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl.
Further, in described step (3), siliceous reactant is SiX
4, SiHX
3, SiH
2x
2, SiH
3x, Si
2x
6, (CH
3)
3siX, (CH
3)
2siX
2, (CH
3) SiX
3, (CH
3)
2siHX, (CH
3) SiH
2x, (CH
3) SiHX
2in one, wherein X=F, Cl, Br or I.
Further, in described step (3) and (5), heat-up rate is 0.5 ~ 1 DEG C/min.
Further, in described step (5), organic amine has following structure: R
7r
8nH, wherein R
7, R
8independently be selected from hydrogen atom, C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl, further R
7, R
8be asynchronously from hydrogen atom.
Further, the reaction mixture that described step (4) or (5) obtain filters, and after filtrate is concentrated, then carries out low temperature crystallization, or underpressure distillation obtains described containing N amidino groups silicon compound; The condition that described filtrate is concentrated is: at 20 ~ 50 DEG C of concentrating under reduced pressure, and concentrated or underpressure distillation pressure is-0.1 ~-0.01MPa.
Further, by chemical vapour deposition (CVD) or ald (ALD) technique, preparation silicon-containing film.
Further, above-mentioned depositing temperature is 30 ~ 900 DEG C.
Further, described reactant gases can be one or more mixed gass formed in himself and nitrogen, hydrogen, argon gas.
Further, described film is that one or more adopting in proplastid as claimed in claim 1 and ammonia, nitrous oxide, nitrogen protoxide, oxygen, ozone, water vapour are reacted and obtained.
Further, described film comprises silicon nitride, containing the silicon oxide of carbonitride of silicium, silicon oxynitride, silicon carbide, silicon oxide, carbon doping and the silicon oxynitride film of carbon doping.
Further, above-mentioned deposit film technique, the preferential cyclic chemical vapor deposition by use low-pressure chemical vapor deposition, hot-wire chemical gas-phase deposition, ald, the ald of plasma enhancing, the chemical vapour deposition of plasma enhancing and plasma enhancing carries out.
Beneficial effect of the present invention comprises:
(1) synthesis condition is gentle, reduces the synthesis cost of front material;
(2) at toluene, ether, methylene dichloride, tetrahydrofuran (THF), has good solvability in the organic solvents such as normal hexane, makes transportation of materials, conveying, the course of processing become simple and easy to operate;
(3) this proplastid material non-toxic, lively type are moderate, and danger coefficient reduces greatly;
(4) have good volatility and thermostability, as through thermogravimetric (TG) method to the test of material thermal property, under normal pressure, there is following structure
proplastid, its T50 is 80 DEG C, and Minimum Residual surplus reaches 0%, (see Fig. 1);
(5) there is good film forming properties, still for above-mentioned proplastid, with N
2/ H
2mixed gas is carrier gas and reacts, and under 600 DEG C of conditions, can form good cvd film, the scanning electron microscope (SEM) photograph of prepared film is shown in Fig. 2.
Accompanying drawing explanation
Technical scheme of the present invention is described in detail referring to accompanying drawing, wherein:
Fig. 1 is for having structural formula
the TG collection of illustrative plates of proplastid, X-coordinate is temperature, and unit is DEG C, and ordinate zou is rate of weight loss, and unit is %.
Fig. 2 is for having structural formula
cVD film scanning Electronic Speculum (SEM) figure of proplastid.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, the invention will be further described.
Preparation method containing N amidino groups silicon compound of the present invention, is undertaken by formula I reaction:
Wherein R
1be selected from C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl ,-N (SiMe
3)
2or-N (R
5r
6), wherein R
2, R
3independently be selected from C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl, wherein R
4, R
5, R
6independently be selected from hydrogen atom, halogen atom (F, Cl, Br, I), C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl ,-Si (R
2r
3r
4),
or-N (R
7r
8), wherein R
5, R
6independently be selected from hydrogen atom, C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl, wherein R
7, R
8independently be selected from hydrogen atom, C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl, wherein R
7, R
8it is asynchronously hydrogen atom;
Wherein there is structure R
1the ether of Li or hexane solution, further R
1be selected from C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl ,-N (SiMe
3)
2or-N (R
5r
6), wherein R
5, R
6independently be selected from hydrogen atom, C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl;
Wherein siliceous reactant is SiX
4, SiHX
3, SiH
2x
2, SiH
3x, Si
2x
6, (CH
3)
3siX, (CH
3)
2siX
2, (CH
3) SiX
3, (CH
3)
2siHX, (CH
3) SiH
2x, (CH
3) SiHX
2in one, wherein X=F, Cl, Br or I.
Embodiment one: a kind of preparation method containing N amidino groups silicon compound proplastid, comprises the following steps:
(1) will
be dissolved in normal hexane solvent,
be 1:10 with the mass ratio of normal hexane solvent, under keeping at-78 DEG C the condition stirred, add LiNiPr
2diethyl ether solution in,
with LiNiPr
2mol ratio be 1:1, LiNiPr
2the concentration of diethyl ether solution be 1.0M, stirring velocity is 800 revs/min; Continue stirring reaction after returning to room temperature 0.5 hour, obtain reaction mixture;
(2) reaction mixture step (1) obtained filters, and collect filter residue, obtain lithium salts solid, mixed by lithium salts solid with normal hexane, the mass ratio of lithium salts solid and normal hexane is 1:10, obtains the hexane solution of lithium salts;
(3) at 0 DEG C according to lithium salts and SiH
2cl
2mol ratio 2:1, is added drop-wise to two SiH by the hexane solution of lithium salts
2cl
2hexane solution in, be slowly warming up to room temperature, heat-up rate is 0.5 DEG C/min, at room temperature continues stirring reaction 10 hours;
(4) filtered by the reaction mixture that step (3) obtains, after the lower 20 DEG C of concentrating under reduced pressure filtrates of-0.01MPa ,-29 DEG C obtain target product after recrystallization repeatedly, and structural formula is:
productive rate: 73%, fusing point: 149 ~ 152 DEG C.
Embodiment two: a kind of preparation method containing N amidino groups silicon compound proplastid, comprises the following steps:
(1) will
be dissolved in toluene solvant,
be 1:15 with the mass ratio of toluene solvant, add in the hexane solution of tert-butyl lithium under keeping at-39 DEG C the condition stirred,
be 1:1.1 with the mol ratio of tert-butyl lithium, the concentration of the hexane solution of tert-butyl lithium is 1.5M, and stirring velocity is 1500 revs/min; Continue stirring reaction after returning to room temperature 1.5 hours, obtain reaction mixture;
(2) reaction mixture step (1) obtained filters, and collect filter residue, obtain lithium salts solid, mixed by lithium salts solid with toluene, the mass ratio of lithium salts solid and toluene is 1:20, obtains the toluene solution of lithium salts;
(3) at-78 DEG C according to lithium salts and SiF
4mol ratio 1:1, is added drop-wise to SiF by the toluene solution of lithium salts
4toluene solution in, be slowly warming up to 110 DEG C, heat-up rate is 1 DEG C/min, continues stirring reaction 7 hours at 110 DEG C;
(4) room temperature is returned to, add the TERTIARY BUTYL AMINE of 6 molar equivalents, slowly rise to 110 DEG C, continue stirring reaction at this temperature again 5 hours, the reaction mixture obtained is filtered, after the lower 30 DEG C of concentrating under reduced pressure filtrates of-0.04MPa, after 0 DEG C repeatedly recrystallization, obtain target product, structural formula is:
productive rate: 89%, fusing point: 199 ~ 201 DEG C.
Embodiment three: a kind of preparation method containing N amidino groups silicon compound proplastid, comprises the following steps:
(1) will
be dissolved in ether solvent,
be 1:20 with the mass ratio of ether, add in the diethyl ether solution of lithium methide under keeping at-53 DEG C the condition stirred,
be 1:1.2 with the mol ratio of phenyl lithium, the concentration of the diethyl ether solution of lithium methide is 2.5M, and stirring velocity is 2000 revs/min; Continue stirring reaction after returning to room temperature 2 hours, obtain reaction mixture;
(2) reaction mixture step (1) obtained filters, and collect filter residue, obtain lithium salts solid, mixed by lithium salts solid with ether, the mass ratio of lithium salts solid and ether is 1:15, obtains the diethyl ether solution of lithium salts;
(3) at 30 DEG C according to lithium salts and SiF
4mol ratio 4:1, is added drop-wise to SiF by the diethyl ether solution of lithium salts
4diethyl ether solution in, continue stirring reaction 5 hours at this temperature;
(4) filtered by the reaction mixture that step (3) obtains, after the lower 40 DEG C of concentrating under reduced pressure filtrates of-0.07MPa, under-0.1MPa, underpressure distillation obtains target product, and structural formula is:
productive rate: 75%.
Embodiment four: a kind of preparation method containing N amidino groups silicon compound proplastid, comprises the following steps:
(1) will
be dissolved in tetrahydrofuran solvent,
be 1:20 with the mass ratio of tetrahydrofuran solvent, add in the diethyl ether solution of phenyl lithium under keeping at 0 DEG C the condition stirred,
be 1:1.2 with the mol ratio of phenyl lithium, the concentration of the diethyl ether solution of phenyl lithium is 2.5M, and stirring velocity is 2000 revs/min; Continue stirring reaction after returning to room temperature 3 hours, obtain reaction mixture;
(2) reaction mixture step (1) obtained filters, and collect filter residue, obtain lithium salts solid, mixed by lithium salts solid with tetrahydrofuran (THF), the mass ratio of lithium salts solid and ether is 1:15, obtains the tetrahydrofuran solution of lithium salts;
(3) at 34 DEG C according to lithium salts and (CH
3)
3siI mol ratio 1:1, is added drop-wise to (CH by the tetrahydrofuran solution of lithium salts
3)
3in the tetrahydrofuran solution of SiI, continue stirring reaction 3 hours at this temperature;
(4) filtered by the reaction mixture that step (3) obtains, after the lower 50 DEG C of concentrating under reduced pressure filtrates of-0.1MPa, under-0.01MPa, underpressure distillation obtains target product, and structural formula is:
productive rate: 92%.
The proplastid that can be used as CVD/ALD containing N amidine ligand silicon compound that the present invention obtains, by chemical vapour deposition (CVD) or ald (ALD) technique, form the silicon oxynitride film of silicon nitride, silicon oxynitride, silicon carbide, silicon oxide, the silicon nitride of carbon doping, the silicon oxide of carbon doping and carbon doping.Described deposit film technique, further preferably by using low-pressure chemical vapor deposition, hot-wire chemical gas-phase deposition, ald, the ald of plasma enhancing, the cyclic chemical vapor deposition of the chemical vapour deposition of plasma enhancing and plasma enhancing carries out.
The present invention has the following advantages: (1) simple synthetic method, and mild condition greatly reduces the synthesis cost of front material; (2) at toluene, ether, methylene dichloride, tetrahydrofuran (THF), has good solvability in the organic solvents such as normal hexane, makes transportation of materials, conveying, and the course of processing becomes simple and easy to operate; (3) this proplastid material non-toxic, lively type are moderate, and danger coefficient reduces greatly; (4) have good volatility and thermostability, as through thermogravimetric (TG) method to the test of material thermal property, under normal pressure, there is following structure
proplastid, its T50 is 80 DEG C, and Minimum Residual surplus reaches 0%, (see Fig. 1); (5) there is good film forming properties, still for above-mentioned proplastid, with N
2/ H
2mixed gas is carrier gas, and under 600 DEG C of conditions, can form good cvd film, the scanning electron microscope (SEM) photograph of prepared film is shown in Fig. 2.
Claims (10)
1. one kind have logical formula I containing N amidino groups silicon compound:
Wherein R
1be selected from C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl ,-N (SiMe
3)
2or-N (R
5r
6), wherein R
2, R
3independently be selected from C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl, wherein R
4, R
5, R
6independently be selected from hydrogen atom, halogen atom (F, Cl, Br, I), C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl ,-Si (R
2r
3r
4),
or-N (R
7r
8), wherein R
5, R
6independently be selected from hydrogen atom, C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl, wherein R
7, R
8independently be selected from hydrogen atom, C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl, wherein R
7, R
8it is asynchronously hydrogen atom.
2. prepare as claimed in claim 1 containing a method for N amidino groups silicon compound, it is characterized in that, comprise the following steps:
(1) carbodiimide or derivatives thereof is dissolved in reaction solvent, the mass ratio of carbodiimide or derivatives thereof and reaction solvent is 1:10 ~ 1:20, alkane/amido lithium solution is added under keeping at-78 ~ 0 DEG C the condition stirred, the mol ratio of carbodiimide or derivatives thereof and lithium alkylide alkane/amine is 1:1 ~ 1.2, the concentration of alkane/amido lithium solution is 1.0 ~ 2.5M, and stirring velocity is 800 ~ 2000 revs/min; Continue stirring reaction after returning to room temperature 0.5 ~ 3 hour, obtain reaction mixture, described reaction solvent is normal hexane, toluene, methylene dichloride, tetrahydrofuran (THF) or ether;
(2) reaction mixture step (1) obtained filters, collect filter cake, obtain lithium salts solid, lithium salts solid is mixed with organic solvent, the mass ratio of lithium salts solid and organic solvent is 1:10 ~ 20, obtain lithium salt solution, described reaction solvent is normal hexane, toluene, methylene dichloride, tetrahydrofuran (THF) or ether;
(3) at-78 ~ 0 DEG C according to lithium salts and siliceous reactant molar ratio 1 ~ 4:1, siliceous reactant or its above-mentioned solution is dripped in above-mentioned lithium salt solution, slowly rise to certain temperature, described temperature is the reflux temperature of room temperature to solvent for use, continues stirring reaction 3 ~ 10 hours at this temperature;
(4) reaction mixture that step (3) obtains is filtered, filter vacuum concentrate rear low temperature crystallization or underpressure distillation obtain logical formula I containing N amidino groups silicon compound;
(5) or in step (3) stirring after 3 ~ 10 hours, at-78 ~ 0 DEG C, add the organic amine of 1 ~ 10 molar equivalent, slowly rise to certain temperature, described temperature is the reflux temperature of room temperature to solvent for use, continue stirring reaction at this temperature again 3 ~ 10 hours, filter vacuum concentrate rear low temperature crystallization or underpressure distillation obtain logical formula I containing N amidino groups silicon compound.
3. preparation method as claimed in claim 2, is characterized in that: alkane described in step (1)/amido lithium solution is for having structure R
1the ether of Li or hexane solution, wherein R
1be selected from C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl ,-N (SiMe
3)
2or-N (R
5r
6), wherein R
5, R
6independently be selected from hydrogen atom, C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl.
4. preparation method as claimed in claim 2, it is characterized in that: in described step (3), siliceous reactant is SiX
4, SiHX
3, SiH
2x
2, SiH
3x, Si
2x
6, (CH
3)
3siX, (CH
3)
2siX
2, (CH
3) SiX
3, (CH
3)
2siHX, (CH
3) SiH
2x, (CH
3) SiHX
2in one, wherein X=F, Cl, Br or I.
5. preparation method as claimed in claim 2, is characterized in that: in described step (3) and (5), heat-up rate is 0.5 ~ 1 DEG C/min.
6. preparation method as claimed in claim 2, is characterized in that: in described step (5), organic amine has following structure: R
7r
8nH, wherein R
7, R
8independently be selected from hydrogen atom, C
1~ C
10alkyl, C
2~ C
10alkenyl, C
2~ C
10alkynyl group, C
3~ C
10cycloalkyl, C
6~ C
17aryl, further R
7, R
8be asynchronously from hydrogen atom.
7. preparation method as claimed in claim 2, it is characterized in that: the reaction mixture that described step (4) or (5) obtain filters, after filtrate is concentrated, then carry out low temperature crystallization, or underpressure distillation obtains described containing N amidino groups silicon compound; The condition that described filtrate is concentrated is: at 20 ~ 50 DEG C of concentrating under reduced pressure, and concentrated or underpressure distillation pressure is-0.1 ~-0.01MPa.
8. be used as the application of integrated circuit thin-film material proplastid as claimed in claim 1 containing N amidino groups silicon compound, it is characterized in that: by chemical vapour deposition (CVD) or ald (ALD) technique, preparation silicon-containing film.
9. apply as claimed in claim 8, it is characterized in that: described film is that one or more adopting in proplastid as claimed in claim 1 and ammonia, nitrous oxide, nitrogen protoxide, oxygen, ozone, water vapour are reacted and obtained.
10. apply as claimed in claim 8, it is characterized in that: described film comprises silicon nitride, containing the silicon oxide of carbonitride of silicium, silicon oxynitride, silicon carbide, silicon oxide, carbon doping and the silicon oxynitride film of carbon doping.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9371338B2 (en) | 2012-07-20 | 2016-06-21 | American Air Liquide, Inc. | Organosilane precursors for ALD/CVD silicon-containing film applications |
| US9382268B1 (en) | 2013-07-19 | 2016-07-05 | American Air Liquide, Inc. | Sulfur containing organosilane precursors for ALD/CVD silicon-containing film applications |
| WO2016094711A3 (en) * | 2014-12-13 | 2016-10-13 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Organosilane precursors for ald/cvd silicon-containing film applications and methods of using the same |
| US9822132B2 (en) | 2013-07-19 | 2017-11-21 | American Air Liquide, Inc. | Hexacoordinate silicon-containing precursors for ALD/CVD silicon-containing film applications |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013177326A1 (en) * | 2012-05-25 | 2013-11-28 | Advanced Technology Materials, Inc. | Silicon precursors for low temperature ald of silicon-based thin-films |
| CN104080944A (en) * | 2012-07-20 | 2014-10-01 | 乔治洛德方法研究和开发液化空气有限公司 | Organosilane precursors for ALD/CVD silicon-containing film applications |
-
2014
- 2014-11-06 CN CN201410621520.4A patent/CN104341447B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013177326A1 (en) * | 2012-05-25 | 2013-11-28 | Advanced Technology Materials, Inc. | Silicon precursors for low temperature ald of silicon-based thin-films |
| CN104080944A (en) * | 2012-07-20 | 2014-10-01 | 乔治洛德方法研究和开发液化空气有限公司 | Organosilane precursors for ALD/CVD silicon-containing film applications |
Non-Patent Citations (2)
| Title |
|---|
| DARIO LIGUORI等，: "Low-Temperature Polymerization of Olefins in the Presence of Titanium Monoamidinate/MAO Catalyst", 《MACROMOL. CHEM. PHYS.》 * |
| DARIO LIGUORI等，: "Polymerization of Propene and 1,3-Butadiene with Vanadyl(V) Monoamidinate Precatalysts and MAO or Dialkylaluminum Chloride Cocatalysts", 《MACROMOL. CHEM. PHYS.》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9371338B2 (en) | 2012-07-20 | 2016-06-21 | American Air Liquide, Inc. | Organosilane precursors for ALD/CVD silicon-containing film applications |
| US9593133B2 (en) | 2012-07-20 | 2017-03-14 | America Air Liquide, Inc. | Organosilane precursors for ALD/CVD silicon-containing film applications |
| US9938303B2 (en) | 2012-07-20 | 2018-04-10 | American Air Liquide, Inc. | Organosilane precursors for ALD/CVD silicon-containing film applications |
| US9382268B1 (en) | 2013-07-19 | 2016-07-05 | American Air Liquide, Inc. | Sulfur containing organosilane precursors for ALD/CVD silicon-containing film applications |
| US9822132B2 (en) | 2013-07-19 | 2017-11-21 | American Air Liquide, Inc. | Hexacoordinate silicon-containing precursors for ALD/CVD silicon-containing film applications |
| WO2016094711A3 (en) * | 2014-12-13 | 2016-10-13 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Organosilane precursors for ald/cvd silicon-containing film applications and methods of using the same |
| US10570513B2 (en) | 2014-12-13 | 2020-02-25 | American Air Liquide, Inc. | Organosilane precursors for ALD/CVD silicon-containing film applications and methods of using the same |
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