CN102093400B - Tetra(orthoalkoxyphenoxy)hafnium, synthetic method thereof and application thereof - Google Patents
Tetra(orthoalkoxyphenoxy)hafnium, synthetic method thereof and application thereof Download PDFInfo
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- CN102093400B CN102093400B CN201010598837.2A CN201010598837A CN102093400B CN 102093400 B CN102093400 B CN 102093400B CN 201010598837 A CN201010598837 A CN 201010598837A CN 102093400 B CN102093400 B CN 102093400B
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- hafnium
- phenoxy group
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- orthoalkoxyphenoxy
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- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 23
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000010189 synthetic method Methods 0.000 title abstract description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- -1 filter Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical class Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical class COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 5
- 150000002363 hafnium compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000005641 tunneling Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
The invention relates to tetra(orthoalkoxyphenoxy)hafnium, a synthetic method thereof and application thereof. The molecule of the tetra(orthoalkoxyphenoxy)hafnium is L4Hf, wherein L is an orthoalkoxyphenol compound. The structural formula of the tetra(orthoalkoxyphenoxy)hafnium is shown as the specifications, wherein R is alkyl.
Description
One, technical field
The present invention relates to a kind of a metal-organic complex and synthetic method thereof in the chemical field, relate to a kind of four (o-alkoxyl phenoxy group) hafnium and synthetic method and application by it.
Two, background technology
Along with the development of semiconductor manufacturing industry, when the characteristic dimension of MOS device dimensions shrink to 0. 1 μ m was following, the gate medium equivalent oxide thickness was little of nanometer scale.At this moment the Direct Tunneling Effect of electronics has a strong impact on stability and the reliability of device with highly significant.Therefore, need to seek novel high K dielectric material, when keeping and increasing grid capacitance, make medium layer still keep enough physical thickness to limit the impact of tunneling effect.
Hafnium is based on a kind of element of hafnium by name, rather than silicon-dioxide in the past; Transistor gate then is comprised of two kinds of metallic elements, has replaced silicon.Hafnium is No. 72 elements in the periodic table of elements, also is a kind of metallic substance.It is silver gray, has very high toughness and preservative property, and chemical property is similar to zirconium.Adopting hafnium to replace silicon-dioxide in 45 nano-transistors, is because hafnium is the material of a kind of thicker (thicker), and it can when significantly reducing electrical leakage quantity, keep high capacitance to realize transistorized high-performance.This innovative technology guides us to release 45 nanometered disposal devices of new generation, and lays a good foundation for we produce the smaller and more exquisite treater of volume in the future.And may directly open the path that leads to 32 nanometers and 22 nanometers thus, clear away the large obstacle of one in the Technology.
Development four (o-alkoxyl phenoxy group) hafnium compound carries out for the purposes of above high K presoma just.At present report to can be used for the grow alkoxyl group hafnium compound of high k material fairly simple.After in molecule, importing the new group that may participate in coordination, can by regulating substituent size, obtain the suitable ligand compound of structure, thereby can better be applied in the hafnium material preparation.Simultaneously, because intramolecular coordination can obtain novel organic hafnium compound that metal center is well covered, such compound is conducive to the volatilization of molecule because intermolecular effect weakens.This just need to be in the design of the title complex of new texture, syntheticly further explore.
Three, summary of the invention
Goal of the invention:A kind of four (o-alkoxyl phenoxy group) hafnium and synthetic method and application, this hafnium compound is the presoma of hafnium, it makes medium layer still keep enough physical thickness to limit the impact of tunneling effect when keeping and increasing grid capacitance.
Technical scheme:Organic hafnium material of the present invention, but for having the phenoxy group hafnium compounds of coordinating group in the molecule, its structure is: L
4Hf, wherein L is the O--Alkoxy phenols compounds, its general structure is as follows:
Substituent R is alkyl.
The method for preparing claim 1 described four (o-alkoxyl phenoxy group) hafnium, it is characterized in that preparation process is: under inert atmosphere, in reaction flask, in toluene solvant, react the sodium salt of making by sodium Metal 99.5 and O--Alkoxy phenols, keep temperature of reaction between 30～70 ℃, then, according to the sodium phenolate mol ratio be the ratio of 1:4, in mentioned solution, add the hafnium tetrachloride solid in batches, after adding, keep system temperature between 50～90 ℃, stirring reaction 3-8 hour, then system is cooled to room temperature, under nitrogen atmosphere, filters reaction mixture, the filtrate that obtains is concentrated into about 25mL, separate out a large amount of white solids, filter, filter cake is washed 2～3 times with normal hexane, vacuum-drying gets white crystal and is four (o-alkoxyl phenoxy group) hafnium.
Four (o-alkoxyl phenoxy group) hafnium is used for the preparation of hafnium as presoma.
Beneficial effect:The characteristics of the hafnium compound that this class is novel are, in molecule, imported alkoxy base after, can by regulating the size of hydrocarbyl group, obtain the suitable ligand compound of structure, thereby can better be applied in the hafnium material preparation.Simultaneously, because intramolecular coordination can obtain organic hafnium compound that metal center is well covered, such compound has not only increased the stability of compound, and because intermolecular effect weakens, is conducive to the volatilization of molecule.
Four, embodiment
Embodiment 1:
Synthesizing of four (O-methoxy phenoxy group) hafnium
Under nitrogen atmosphere, add sodium and the 250mL toluene that 4.6 g are cut into piece in the 500mL three-necked bottle, mechanical stirring to wherein slowly adding 24.8 g hydroxyanisoles, keeps temperature of reaction between 30～70 ℃, stirring reaction 0.5～2 hour.Then, 15.9 g hafnium tetrachlorides are added in the three-necked bottle in batches, add in 30 minutes.After adding, keep system temperature between 50～90 ℃, then stirring reaction 5 hours is cooled to room temperature with system.
Under nitrogen atmosphere, filter reaction mixture, the filtrate that obtains is concentrated into about 25mL, separate out a large amount of white solids, filter, filter cake is washed 2～3 times with normal hexane, and vacuum-drying gets white crystal, productive rate 80～90%.Product has passed through the evaluation of nucleus magnetic hydrogen spectrum.
1H NMR (CDCl
3, 300 MHz): 6.89-6.96 (m, 4H), 6.67-6.77 (m, 12H), 3.91 (s, 12H)。
Claims (1)
1. the method for preparing four (O-methoxy phenoxy group) hafnium, it is characterized in that preparation process is: under nitrogen atmosphere, add sodium and the 250mL toluene that 4.6 g are cut into piece in the 500mL three-necked bottle, mechanical stirring, to wherein slowly adding 24.8 g hydroxyanisoles, keep temperature of reaction between 30～70 ℃, stirring reaction 0.5～2 hour; Then, 15.9 g hafnium tetrachlorides are added in the three-necked bottle in batches, add in 30 minutes; After adding, keep system temperature between 50～90 ℃, then stirring reaction 5 hours is cooled to room temperature with system; Under nitrogen atmosphere, filter reaction mixture, the filtrate that obtains is concentrated into about 25mL, separate out a large amount of white solids, filter, filter cake is washed 2～3 times with normal hexane, and vacuum-drying gets white crystal and is four (O-methoxy phenoxy group) hafnium.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010598837.2A CN102093400B (en) | 2010-12-22 | 2010-12-22 | Tetra(orthoalkoxyphenoxy)hafnium, synthetic method thereof and application thereof |
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| CN201010598837.2A CN102093400B (en) | 2010-12-22 | 2010-12-22 | Tetra(orthoalkoxyphenoxy)hafnium, synthetic method thereof and application thereof |
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| Publication Number | Publication Date |
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| CN102093400A CN102093400A (en) | 2011-06-15 |
| CN102093400B true CN102093400B (en) | 2013-03-13 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1265747A (en) * | 1969-05-28 | 1972-03-08 | ||
| CN101460509A (en) * | 2006-05-05 | 2009-06-17 | 陶氏环球技术公司 | Ortho-metallated hafnium complexes of imidazole ligands |
-
2010
- 2010-12-22 CN CN201010598837.2A patent/CN102093400B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1265747A (en) * | 1969-05-28 | 1972-03-08 | ||
| CN101460509A (en) * | 2006-05-05 | 2009-06-17 | 陶氏环球技术公司 | Ortho-metallated hafnium complexes of imidazole ligands |
Non-Patent Citations (2)
| Title |
|---|
| Hideo Matsui et al.Syntheses and electronic behaviors of net-worked, alternating hafnium-organic moiety hybrid copolymers.《J Mater Sci》.2007,第42卷3964–3968. * |
| HideoMatsuietal.Synthesesandelectronicbehaviorsofnet-worked alternating hafnium-organic moiety hybrid copolymers.《J Mater Sci》.2007 |
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| CN102093400A (en) | 2011-06-15 |
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