CN102351891B - Method for synthesizing hafnium tetra-tert-butoxide - Google Patents
Method for synthesizing hafnium tetra-tert-butoxide Download PDFInfo
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- CN102351891B CN102351891B CN201110254613.4A CN201110254613A CN102351891B CN 102351891 B CN102351891 B CN 102351891B CN 201110254613 A CN201110254613 A CN 201110254613A CN 102351891 B CN102351891 B CN 102351891B
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- tert
- hafnium
- butoxide
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- 238000000034 method Methods 0.000 title abstract description 12
- WZVIPWQGBBCHJP-UHFFFAOYSA-N hafnium(4+);2-methylpropan-2-olate Chemical compound [Hf+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] WZVIPWQGBBCHJP-UHFFFAOYSA-N 0.000 title abstract 2
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims abstract description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 238000010189 synthetic method Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 abstract description 9
- 238000003756 stirring Methods 0.000 abstract description 8
- -1 hafnium tetra-tert-butoxide compound Chemical class 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003989 dielectric material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
The invention relates to a method for synthesizing hafnium tetra-tert-butoxide, which comprises the following steps of: adding potassium tert-butoxide and n-hexane into a three-necked bottle in nitrogen atmosphere, and uniformly stirring; adding hafnium tetrachloride into a reaction system in a molar ratio of the hafnium tetrachloride to the potassium tert-butoxide of 1:4.4-1:4.8, and keeping the temperature of the reaction system to be between 20 and 60 DEG C; keeping the temperature of the reaction system to be between 40 and 65 DEG C after the hafnium tetrachloride is completely added, and reacting for 6 to 10 hours with stirring under the protection of inert gas; removing a reacted solvent under one atmospheric pressure, distilling under reduced pressure after the solvent n-hexane is completely removed, and collecting 90 to 92 DEG C/5mmHg fractions, namely a hafnium tetra-tert-butoxide compound. Simple and readily available raw materials, namely the potassium tert-butoxide and the hafnium tetrachloride are reacted, the method is easy to operate, and cost is reduced.
Description
Technical field
The present invention relates to the synthetic method of a metal-organic complex in chemical field, particularly relate to a kind of synthetic method of four tert.-butoxy hafniums.
Background technology
Along with the progress of technology, the size of CMOS transistor is more and more less, integrated level is more and more higher. and current lithographic dimension reaches 45nm, CMOS grid equivalent oxide thickness drops to below lnm, the thickness of gate oxide is close to interatomic distance, the reduction of equivalent oxide thickness can cause tunnel effect, larger passage leakage current can cause the high power consumption of chip and corresponding heat dissipation problem, this integrated level to device, reliability and life-span all cause disadvantageous effect, are therefore badly in need of researching and developing the grid medium with high dielectric material that makes new advances to replace traditional SiO
2.
Relative permittivity is greater than 3.9, and the material of the relative permittivity of si (3.9 be) is referred to as high dielectric material (i.e. hafnium).Existing gate medium SiO is replaced with high dielectric material
2, while maintenance same capacitance density, gate medium can have larger physical thickness, thus avoids at ultra-thin Si O
2the leakage problem that in gate medium, tunnelling causes.Can within the several years the existing performance of retainer member, maintain reducing further of transistor dimensions, therefore, domestic and international researchist conducts in-depth research grid medium with high dielectric material.
SiO is replaced at the suitable material of selection
2exploration in, had a lot of material to be attempted.Wherein, specific inductivity and the energy gap of the organic compound of zirconium, hafnium and rare earth element etc. are relatively high, substantially meet the requirement of gate dielectric material and cause industry to pay close attention to greatly.
Develop four tert.-butoxy hafnium compounds to carry out for the purposes of above high K presoma just.Be liquid under four tert.-butoxy hafnium normal temperature, having stability and higher saturated vapor pressure relatively preferably, is the one very potential high-g value presoma of tool.The synthesis of the four tert.-butoxy hafnium compounds of reporting for work at present mainly contains three various methodologies: the first is will with HfOCl
2for raw material, first synthesize (C
5h
6n)
2.HfCl
6intermediate, then obtains alkoxyl group hafnium compound.This method needs by pyridine complex intermediate, and condition is harsher.Second method is at NH
3under existent condition, be that raw material is to synthesize last alkoxyl group hafnium compound with hafnium tetrachloride.This method needs to carry out under ammonia existent condition, and this brings certain trouble to operation.The third first will synthesize four organic amine compounds, and then react with the trimethyl carbinol and obtain.First this method will synthesize four organic amine compounds, and first this need separation and purification, and then reacts, and this not only needs two steps just can be synthesized to last compound, complex operation, and can make to reduce by productive rate.Although so there has been the synthesis about four tert.-butoxy hafniums, method also needs to improve, under simple condition, four tert.-butoxy class hafnium compounds can be synthesized from raw material simple and easy to get.
Summary of the invention
the technical problem solved:the present invention, mainly for the deficiency of the synthetic method of four tert.-butoxy hafniums in currently available technology, provides a kind of novel synthetic method.The method, first from potassium tert.-butoxide simple and easy to get, then with solid hafnium tetrachloride direct reaction, not only more efficiently can obtain target product, can also reduce reaction cost, simplifies operation.Reaction uses varsol as solvent, directly except distillation after desolventizing just can obtain finally obtaining compound after reaction terminates.
technical scheme:
Four tert.-butoxy hafnium compounds of the present invention have following structure:
Four tert.-butoxy hafniums (Hf (OC (Me)
3)
4) be liquid source under room temperature, boiling point: 90 DEG C/5 mmHg
The synthetic method of four tert.-butoxy hafniums, step is:
(1) under nitrogen atmosphere, in the ratio adding 100 ~ 400 ml n-hexanes in every 50 grams of potassium tert.-butoxides, add potassium tert.-butoxide and normal hexane in three-necked bottle, stir;
(2) by hafnium tetrachloride: potassium tert.-butoxide is the mol ratio of 1:4.4 ~ 1:4.8, hafnium tetrachloride is joined in above-mentioned reaction system, keep the temperature of reaction system between 20 to 60 DEG C; After adding hafnium tetrachloride, the temperature of reaction system is allowed to remain between 40-65 DEG C, stirring reaction 6-10 hour under the condition of protection of inert gas;
(3) then remove the solvent of reaction under a normal atmosphere, after equal solvent normal hexane all removes, underpressure distillation, collects the cut of 90-92 DEG C/5 mmHg, is four tert.-butoxy hafnium compounds.
beneficial effect:
(1) reaction obtains raw material potassium tert.-butoxide and hafnium tetrachloride from simple and easy to get, simple to operate, and reduces cost.
(2) in reaction, solid hafnium tetrachloride can directly join in reaction system, makes to react operation is very easy.
(3) reaction uses the simple hydro carbons that obtains as solvent, not only reduces the cost of reaction, and greatly reduces the toxicity of reaction.
(4) in the preparation process of four tert.-butoxy hafniums, without the need to adding ammonia, the toxicity of reaction is reduced.
(5) post-reaction treatment is very simple, directly except distillation after desolventizing just can obtain final product, and without the need to filtering in the last handling process of reaction, and straight run distillation, this just enormously simplify the operation of reaction, and the loss that can greatly reduce in last handling process, the productive rate of reaction can be improved.
Embodiment
The synthesis of embodiment 1: four tert.-butoxy hafnium
(1) under nitrogen atmosphere, 49.2 grams of potassium tert.-butoxides and 200 mL normal hexanes are added in 500mL three-necked bottle, mechanical stirring.
(2) 32 grams of hafnium tetrachlorides are joined in above-mentioned reaction system in batches, keep the temperature of reaction system not higher than 60 DEG C.After adding hafnium tetrachloride, allow the temperature of reaction system remain between 40-65 DEG C, under the condition of mechanical stirring protection of inert gas, react 6-10 hour.
(3) then remove the solvent of reaction under normal pressure, after equal solvent normal hexane all removes, underpressure distillation, collects the cut of 90-92 DEG C/5 mmHg, is four tert.-butoxy hafnium compounds.Productive rate is 80-93%.Product have passed the qualification of nucleus magnetic hydrogen spectrum.
1H NMR (300 MHz, CDCl
3): 1.38 (s, 36H).
Embodiment 2:
The synthetic method of four tert.-butoxy hafniums, step is:
(1) under nitrogen atmosphere, add 49.2 grams of potassium tert.-butoxides and 200 mL normal hexanes in 500mL three-necked bottle, stir;
(2) by by hafnium tetrachloride: potassium tert.-butoxide is that the hafnium tetrachloride of 1:4.4 mol ratio joins in above-mentioned reaction system, keep the temperature of reaction system at 20 DEG C; After adding hafnium tetrachloride, the temperature of reaction system is allowed to remain on 40 DEG C, stirring reaction 10 hours under the condition of protection of inert gas;
(3) then remove the solvent of reaction under a normal atmosphere, after equal solvent normal hexane all removes, underpressure distillation, collects the cut of 90-92 DEG C/5 mmHg, is four tert.-butoxy hafnium compounds.Product have passed the qualification of nucleus magnetic hydrogen spectrum.
1H NMR (300 MHz, CDCl
3): 1.38 (s, 36H).
Embodiment 3:
The synthetic method of four tert.-butoxy hafniums, step is:
(1) under nitrogen atmosphere, add 49.2 grams of potassium tert.-butoxides and 200 mL normal hexanes in 500mL three-necked bottle, stir;
(2) by by hafnium tetrachloride: potassium tert.-butoxide is that the hafnium tetrachloride of 1:4.8 mol ratio joins in above-mentioned reaction system, keep the temperature of reaction system at 60 DEG C; After adding hafnium tetrachloride, the temperature of reaction system is allowed to remain on 65 DEG C, stirring reaction 6 hours under the condition of protection of inert gas;
(3) then remove the solvent of reaction under a normal atmosphere, after equal solvent normal hexane all removes, underpressure distillation, collects the cut of 90-92 DEG C/5 mmHg, is four tert.-butoxy hafnium compounds.Product have passed the qualification of nucleus magnetic hydrogen spectrum.
1H NMR (300 MHz, CDCl
3): 1.38 (s, 36H).
Claims (1)
1. the synthetic method of four tert.-butoxy hafniums, is characterized in that step is:
(1) under nitrogen atmosphere, 49.2 grams of potassium tert.-butoxides and 200 mL normal hexanes are added in 500mL three-necked bottle, mechanical stirring;
(2) 32 grams of hafnium tetrachlorides are joined in above-mentioned reaction system in batches, keep the temperature of reaction system not higher than 60 DEG C; After adding hafnium tetrachloride, allow the temperature of reaction system remain between 40-65 DEG C, under the condition of mechanical stirring protection of inert gas, react 6-10 hour;
(3) then remove the solvent of reaction under normal pressure, after equal solvent normal hexane all removes, underpressure distillation, collects the cut of 90-92 DEG C/5 mmHg, is four tert.-butoxy hafnium compounds.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110254613.4A CN102351891B (en) | 2011-08-31 | 2011-08-31 | Method for synthesizing hafnium tetra-tert-butoxide |
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|---|---|---|---|
| CN201110254613.4A CN102351891B (en) | 2011-08-31 | 2011-08-31 | Method for synthesizing hafnium tetra-tert-butoxide |
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| CN102351891B true CN102351891B (en) | 2015-03-18 |
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Granted publication date: 20150318 Termination date: 20210831 |