CN102040478B - Synthesis method of hafnium tetraethoxide - Google Patents
Synthesis method of hafnium tetraethoxide Download PDFInfo
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- CN102040478B CN102040478B CN2010105988921A CN201010598892A CN102040478B CN 102040478 B CN102040478 B CN 102040478B CN 2010105988921 A CN2010105988921 A CN 2010105988921A CN 201010598892 A CN201010598892 A CN 201010598892A CN 102040478 B CN102040478 B CN 102040478B
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- hafnium
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- BFIMXCBKRLYJQO-UHFFFAOYSA-N ethanolate;hafnium(4+) Chemical compound [Hf+4].CC[O-].CC[O-].CC[O-].CC[O-] BFIMXCBKRLYJQO-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 10
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 10
- 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 abstract description 8
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 238000010189 synthetic method Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- -1 alkoxyl group hafnium compound Chemical class 0.000 description 5
- 229910052735 hafnium Inorganic materials 0.000 description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
The invention relates to a synthesis method of hafnium tetraethoxide, which comprises the following steps: (1) in a nitrogen atmosphere, adding 5.8g of diced sodium and 100mL of ethanol into a 500mL three-necked bottle, mechanically stirring until the sodium completely reacts, and cooling to room temperature; adding 16g of hafnium tetrachloride into the reaction system in batches while keeping the temperature of the reaction system not higher than 60 DEG C; after adding the hafnium tetrachloride, keeping the temperature of the reaction system at 40-65 DEG C, reacting for 2-8 hours under the condition of mechanical stirring, and evaporating out the residual ethanol to obtain a dry solid; and adding 150mL of phenylmethane to the solid, stirring, filtering, concentrating the filtrate to precipitate white solids, and drying the white solids in vacuum to obtain white crystals. The yield of the method is 80-85%.
Description
Technical field
The present invention relates to a metal-organic complex in the chemical field, relate in particular to a kind of synthetic method of tetraethoxy hafnium.
Background technology
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.
What is high-k and the field-effect of material about? be exactly that material should have good insulation attribute, produce good field-effect in (between source electrode and the drain electrode) between the passage on grid and the crystalline silicon substrate simultaneously--be exactly height-K.High insulation attribute and height-K attribute all is the transistorized desirable attributes of high-performance.K is the engineering term of electronics in fact, and K comes from Greek Kappa, is used for weighing the ability of a kind of material stored charge (positive charge or negatron), and the material with high K can be than other materials stored charge better.
The semi-conductor industry has predicted 45 nanometer processing procedures before for many years and can arrive one day, has only to substitute traditional silicon-dioxide with the high K medium material and just can cross difficult barriers.Because adopt the high K medium material, (k of SiO is 3.9, and high k material is more than 20) is equivalent to promote the net thickness of grid theoretically, and leakage current is dropped to below 10%.In addition, the polysilicon gate material common and traditional owing to the work function of high k material do not mate, thus must substitute with metal gate electrode, the therefore combination of high k and metal gate material, oneself becomes the watershed of the new CMOS structure of 45 nanometer processing procedures.Because 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 tetraethoxy hafnium compound carries out for the purposes of above high K presoma just.The tetraethoxy hafnium compound of reporting for work at present synthetic mainly contains two kinds of methods: the first is will be with HfOCl
2Be raw material, at first synthesize (C
5H
6N)
2.HfCl
6Then intermediate obtains the alkoxyl group hafnium compound.This method need to be passed through the pyridine complex intermediate, and condition is relatively harsher.Second method is under the condition that NH3 exists, and synthesizes last alkoxyl group hafnium compound take hafnium tetrachloride as raw material.This method need to be carried out under the condition that ammonia exists, and this brings certain trouble to operation.Although so synthetic relevant for the tetraethoxy hafnium, method also needs to improve, in order to can under simple condition, synthesize four alkoxyl group class hafnium compounds from the raw material that simply is easy to get.
Summary of the invention
Goal of the invention:The invention provides a kind of synthetic method of tetraethoxy hafnium.The method is the sodium alkoxide from simply being easy to get at first, then with the reaction of solid hafnium tetrachloride, not only can obtain more efficiently target product, can also reduce reaction cost, simplifies operation.
Technical scheme:A kind of synthetic method of tetraethoxy hafnium, synthesis step is: (1) adds sodium and the 100 mL ethanol that 5.8 g are cut into small pieces in the 500 mL three-necked bottles under nitrogen atmosphere, mechanical stirring until the sodium complete reaction is complete, then is cooled to room temperature; 16 gram hafnium tetrachlorides are joined in the above-mentioned reaction system in batches, keep the temperature of reaction system not to be higher than 60 ℃.After adding hafnium tetrachloride, allow the temperature of reaction system remain between 40-65 ℃, reaction is 2-8 hour under the mechanical stirring condition, then steams remaining ethanol to doing; Then add 150mL toluene in this solid, filter after stirring, filtrate is concentrated, separates out white solid, and vacuum-drying gets white crystal, productive rate 80-85%wt.
Tetraethoxy hafnium compound of the present invention has following structure (RO)
4Hf, general structure is as follows:
Wherein, R=Et.
Beneficial effect:
(1) react from sodium alkoxide, simple to operate.
(2) in the preparation process of tetraethoxy hafnium, need not to add ammonia, reduced the toxicity of reaction.
(3) post-reaction treatment, simple filter operation just can obtain corresponding product.
Embodiment
Embodiment 1
Synthesizing of tetraethoxy hafnium
(1) under nitrogen atmosphere, add sodium and the 100 mL ethanol that 5.8 g are cut into small pieces in the 500 mL three-necked bottles, mechanical stirring until the sodium complete reaction is complete, then is cooled to room temperature.
(2) 16 gram hafnium tetrachlorides are joined in the above-mentioned reaction system in batches, keep the temperature of reaction system not to be higher than 60 ℃.After adding hafnium tetrachloride, allow the temperature of reaction system remain between 40-65 ℃, reaction is 2-8 hour under the mechanical stirring condition, then steams remaining ethanol to doing.
(3) then add 150mL toluene in this solid, filter after stirring, filtrate is concentrated, separates out white solid, and vacuum-drying gets white crystal, productive rate 80-85%wt.Product has passed through the evaluation of nucleus magnetic hydrogen spectrum.
1H?NMR?(CDCl
3,?300?MHz):?4.08-4.28?(m,?8H),?1.19-1.34?(m,?12H)。
Claims (1)
1. the synthetic method of a tetraethoxy hafnium is characterized in that synthesis step is: (1) adds sodium and the 100 mL ethanol that 5.8 g are cut into small pieces in the 500 mL three-necked bottles under nitrogen atmosphere, mechanical stirring until the sodium complete reaction is complete, then is cooled to room temperature; 16 gram hafnium tetrachlorides are joined in the above-mentioned reaction system in batches, keep the temperature of reaction system not to be higher than 60 ℃; After adding hafnium tetrachloride, allow the temperature of reaction system remain between 40-65 ℃, reaction is 2-8 hour under the mechanical stirring condition, then steams remaining ethanol to doing; Then add 150mL toluene in this solid, filter after stirring, filtrate is concentrated, separates out white solid, and vacuum-drying gets white crystal.
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| CN2010105988921A CN102040478B (en) | 2010-12-22 | 2010-12-22 | Synthesis method of hafnium tetraethoxide |
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|---|---|---|---|
| CN2010105988921A CN102040478B (en) | 2010-12-22 | 2010-12-22 | Synthesis method of hafnium tetraethoxide |
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| CN102040478A CN102040478A (en) | 2011-05-04 |
| CN102040478B true CN102040478B (en) | 2013-03-13 |
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| CN106008224B (en) * | 2016-05-25 | 2018-03-06 | 苏州复纳电子科技有限公司 | One kind four（Methyl ethylamine）The synthetic method of vanadium |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919813A (en) * | 2005-08-27 | 2007-02-28 | H.C.施塔克股份有限公司 | Process for the preparation of high-purity zirconium, hafnium, tantalum and niobium alkoxides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2575562B2 (en) * | 1991-11-25 | 1997-01-29 | 株式会社ジャパンエナジー | Method for purifying tantalum alkoxide |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919813A (en) * | 2005-08-27 | 2007-02-28 | H.C.施塔克股份有限公司 | Process for the preparation of high-purity zirconium, hafnium, tantalum and niobium alkoxides |
Non-Patent Citations (2)
| Title |
|---|
| D.C.Bradley,et al..Hafnium alkoxides.《Journal of the Chemical Society》.1953,1634-1636. * |
| Fritz Bischoff,et al..THE ALKYL TITANATES.《Journal of the American Chemical Society》.1924,第46卷256-259. * |
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Effective date of registration: 20160226 Address after: 210093 Nanjing, Gulou District, Jiangsu, No. 22 Hankou Road Patentee after: Nanjing University Asset Management Co., Ltd. Address before: 210093 Hankou Road, Jiangsu, China, No. 22, No. Patentee before: Nanjing University |
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Effective date of registration: 20160616 Address after: Hankou Road, Gulou District of Nanjing city in Jiangsu province 210093 No. 22 building 1003 Yimin fee Patentee after: NANJING UNIVERSITY TECHNOLOGY PARK DEVELOPMENT CO., LTD. Address before: 210093 Nanjing, Gulou District, Jiangsu, No. 22 Hankou Road Patentee before: Nanjing University Asset Management Co., Ltd. |
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Effective date of registration: 20160713 Address after: 238261 Anhui city of Ma'anshan province Ma'anshan Cheng Po port district town of Huai Lu incubator Park Patentee after: Ma On Shan High Tech Research Institute Co., Ltd. Address before: Hankou Road, Gulou District of Nanjing city in Jiangsu province 210093 No. 22 building 1003 Yimin fee Patentee before: NANJING UNIVERSITY TECHNOLOGY PARK DEVELOPMENT CO., LTD. |