CN102093400A - 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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- CN102093400A CN102093400A CN201010598837.2A CN201010598837A CN102093400A CN 102093400 A CN102093400 A CN 102093400A CN 201010598837 A CN201010598837 A CN 201010598837A CN 102093400 A CN102093400 A CN 102093400A
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- hafnium
- alkoxyl
- phenoxy group
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- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 26
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000010189 synthetic method Methods 0.000 title abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 6
- -1 filter Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000003756 stirring Methods 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 compound 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
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical class COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 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
- 230000008676 import Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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 continuous 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 the 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 influence 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 made up 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 keep high capacitance to realize transistorized high-performance when significantly reducing electrical leakage quantity.This innovative technology guides us to release 45 nanometer treaters 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 big obstacle of one in the Technology.
Development four (o-alkoxyl phenoxy group) hafnium compound carries out at 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.Intramolecularly import new may participate in the coordinate group after, can obtain the suitable ligand compound of structure, thereby can better be applied in the preparation of hafnium material by regulating substituent size.Simultaneously, because intramolecular coordination can obtain novel organic hafnium compound that metal center is well covered, such compound helps the volatilization of molecule because intermolecular effect weakens.This just need further explore in the design of the title complex of new texture, on synthetic.
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 influence of tunneling effect when keeping and increasing grid capacitance.
Technical scheme:Organic hafnium material of the present invention, but for intramolecularly has the phenoxy group hafnium compounds of coordinating group, its structure is: L
4Hf, wherein L is the o-alkoxyl phenol compound, its general structure is as follows:
Substituent R is an 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-alkoxyl phenol, keep temperature of reaction between 30～70 ℃, then, according to the sodium phenolate mol ratio be the ratio of 1:4, in above-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, 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, 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, after intramolecularly has imported alkoxy base, can obtain the suitable ligand compound of structure, thereby can better be applied in the preparation of hafnium material by regulating the size of hydrocarbyl group.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, helps the volatilization of molecule.
Four, embodiment
Embodiment 1:
Synthesizing of four (O-methoxy phenoxy group) hafnium
Under nitrogen atmosphere, add 4.6 g in the 500mL three-necked bottle and cut caked sodium and 250mL toluene, 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 ℃, stirring reaction 5 hours is cooled to room temperature with system then.
Under nitrogen atmosphere, filter reaction mixture is concentrated into about 25mL with the filtrate that obtains, and separates out a large amount of white solids, filters, and 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 (3)
1. four (o-alkoxyl phenoxy group) hafnium, its molecule is L
4Hf, wherein L is the o-alkoxyl phenol compound, structural formula is as follows:
Wherein R is an alkyl.
2. 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-alkoxyl phenol, keep temperature of reaction between 30～70 ℃, then, according to the sodium phenolate mol ratio be the ratio of 1:4, in above-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, 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, vacuum-drying gets white crystal and is four (o-alkoxyl phenoxy group) hafnium.
3. four (o-alkoxyl phenoxy group) hafnium is used for the preparation of hafnium as presoma.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010598837.2A CN102093400B (en) | 2010-12-22 | 2010-12-22 | Tetra(orthoalkoxyphenoxy)hafnium, synthetic method thereof and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010598837.2A CN102093400B (en) | 2010-12-22 | 2010-12-22 | Tetra(orthoalkoxyphenoxy)hafnium, synthetic method thereof and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102093400A true CN102093400A (en) | 2011-06-15 |
| CN102093400B CN102093400B (en) | 2013-03-13 |
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| CN201010598837.2A Expired - Fee Related CN102093400B (en) | 2010-12-22 | 2010-12-22 | Tetra(orthoalkoxyphenoxy)hafnium, synthetic method thereof and application thereof |
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| Country | Link |
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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 not_active Expired - Fee Related
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 (1)
| Title |
|---|
| 《J Mater Sci》 20070131 Hideo Matsui et al Syntheses and electronic behaviors of net-worked, alternating hafnium-organic moiety hybrid copolymers 3964-3968 1、3 第42卷, * |
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| CN102093400B (en) | 2013-03-13 |
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Granted publication date: 20130313 |