CN102351891A - Method for synthesizing hafnium tetra-tert-butoxide - Google Patents
Method for synthesizing hafnium tetra-tert-butoxide Download PDFInfo
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- CN102351891A CN102351891A CN2011102546134A CN201110254613A CN102351891A CN 102351891 A CN102351891 A CN 102351891A CN 2011102546134 A CN2011102546134 A CN 2011102546134A CN 201110254613 A CN201110254613 A CN 201110254613A CN 102351891 A CN102351891 A CN 102351891A
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- tert
- butoxide
- hafnium
- reaction system
- reaction
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Links
- 238000000034 method Methods 0.000 title abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims abstract description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 19
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 238000001308 synthesis method Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- -1 hafnium tetra-tert-butoxide compound Chemical class 0.000 abstract description 3
- 239000003989 dielectric material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 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
- 238000010907 mechanical stirring Methods 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
- 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
- 238000011161 development 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
- 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
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 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 synthesis method of a metal-organic complex in the chemical field, relate in particular to a kind of synthesis method of four tert.-butoxy hafniums.
Background technology
Along with development of technology; The transistorized size of CMOS is more and more littler; Integrated level is more and more higher. and present lithographic dimension has reached 45nm; CMOS grid equivalent oxide thickness drops to below the lnm; The thickness of gate oxide is near interatomic distance; The reducing of equivalent oxide thickness can cause tunnel effect; Bigger passage leakage current can cause the high power consumption and corresponding heat dissipation problem of chip; This integrated level to device, reliability and life-span have all been caused disadvantageous effect, so the grid medium with high dielectric material that the urgent need research and development make new advances is to replace traditional SiO
2
Relative permittivity is referred to as high dielectric material (being hafnium) greater than the material of 3.9 (3.9 are the relative permittivity of si).Replace existing gate medium SiO with high dielectric material
2, gate medium can have bigger physical thickness when keeping same capacitance density, thereby has avoided at ultra-thin Si O
2The leakage problem that tunnelling causes in the gate medium.Can in the several years, keep the existing performance of device, keep further dwindling of transistor dimensions, therefore, the researchist has carried out deep research to the grid medium with high dielectric material both at home and abroad.
Selecting suitable material to replace SiO
2Exploration in, had a lot of materials to be attempted.Wherein, the specific inductivity of the organic compound of zirconium, hafnium and rare earth element etc. is relative with energy gap higher, meets the requirement of gate dielectric material basically and causes that industry pays close attention to greatly.
Develop four tert.-butoxy hafnium compounds be directed against just more than the purposes of high K presoma carry out.Under the four tert.-butoxy hafnium normal temperature is liquid, has stability and higher saturated vapor pressure relatively preferably, is a kind of high k material presoma of very potentialization.Synthetic three various methodologies that mainly contain of the four tert.-butoxy hafnium compounds of reporting for work at present: first kind is will be with HfOCl
2Be raw material, at first synthesize (C
5H
6N)
2.HfCl
6Intermediate obtains the alkoxyl group hafnium compound then.This method need be passed through the pyridine complex intermediate, and condition is relatively harsher.Second method is at NH
3Under the condition that exists, be that raw material synthesizes last alkoxyl group hafnium compound with the hafnium tetrachloride.This method need be carried out under the condition that ammonia exists, and this brings certain trouble to operation.The third is to synthesize having ideals, morality, culture, and discipline machine aminated compounds earlier, and then makes with trimethyl carbinol reaction.This method at first will be synthesized having ideals, morality, culture, and discipline machine aminated compounds, and this at first needs separation and purification, and then reaction, and this not only needed for two steps just can be synthesized to the last compound that gets, complex operation, and can make and must reduce by productive rate.Though so synthetic relevant for four tert.-butoxy hafniums, method also need be improved, so that can under simple condition, synthesize four tert.-butoxy class hafnium compounds from the raw material that simply is easy to get.
Summary of the invention
The technical problem that solves:The present invention is primarily aimed at the deficiency of the synthesis method of four tert.-butoxy hafniums in the present prior art, and a kind of novel synthesis method is provided.This method is the potassium tert.-butoxide from simply being easy to get at first, with solid hafnium tetrachloride direct reaction, not only can obtain target product more efficiently then, can also reduce reaction cost, simplifies operation.Reaction use varsol is as solvent, and reaction finishes directly to get compound to the end except that the back distillation of desolvating just can get later on.
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 the room temperature, boiling point: 90 ℃/5 mmHg
The synthesis method of four tert.-butoxy hafniums, step is:
(1) under nitrogen atmosphere, the ratio in adding 100～400 ml n-hexanes in per 50 gram potassium tert.-butoxides adds potassium tert.-butoxide and normal hexane in the three-necked bottle, stir;
(2) by hafnium tetrachloride: potassium tert.-butoxide is the mol ratio of 1:4.4 ~ 1:4.8, and hafnium tetrachloride is joined in the above-mentioned reaction system, and the temperature that keeps reaction system is between 20 to 60 ℃; After adding hafnium tetrachloride, allow the temperature of reaction system remain between 40-65 ℃, under the condition of protection of inert gas stirring reaction 6-10 hour;
(3) remove the solvent of reaction then under normal atmosphere, after the equal solvent normal hexane was all removed, the cut of 90-92 ℃/5 mmHg was collected in underpressure distillation, is four tert.-butoxy hafnium compounds.
Beneficial effect:
(1) reaction from simply be easy to get raw material potassium tert.-butoxide and hafnium tetrachloride, simple to operate, and reduced cost.
(2) in the reaction, the solid hafnium tetrachloride can directly join in the reaction system, makes to react to such an extent that operation is very easy.
(3) reaction uses the simple hydro carbons that gets as solvent, has not only reduced the cost of reaction, and has greatly reduced the toxicity of reaction.
(4) in the preparation process of four tert.-butoxy hafniums, need not to add ammonia, reduced the toxicity of reaction.
(5) post-reaction treatment is very simple; Directly remove the back distillation of desolvating and just can obtain final product; And need not in the last handling process of reaction to filter; And straight run distillation; This has just simplified the operation of reaction greatly; And can significantly reduce the loss in the last handling process, can improve the productive rate of reaction.
Embodiment
Synthesizing of 1: four tert.-butoxy hafnium of embodiment
(1) under nitrogen atmosphere, adds 49.2 gram potassium tert.-butoxide and 200 mL normal hexanes in the 500mL three-necked bottle, mechanical stirring.
(2) 32 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 6-10 hour under the condition of mechanical stirring protection of inert gas.
(3) remove the solvent of reaction then under the normal pressure, after the equal solvent normal hexane was all removed, the cut of 90-92 ℃/5 mmHg was collected in underpressure distillation, is four tert.-butoxy hafnium compounds.Productive rate is 80-93%.Product has passed through the evaluation of nucleus magnetic hydrogen spectrum.
1H?NMR?(300?MHz,?CDCl
3):?1.38?(s,?36H).
Embodiment 2:
The synthesis method of four tert.-butoxy hafniums, step is:
(1) under nitrogen atmosphere, add 49.2 gram potassium tert.-butoxide and 200 mL normal hexanes in the 500mL three-necked bottle, stir;
(2) will be by hafnium tetrachloride: potassium tert.-butoxide be that the hafnium tetrachloride of 1:4.4 mol ratio joins in the above-mentioned reaction system, and the temperature that keeps reaction system is at 20 ℃; After adding hafnium tetrachloride, allow the temperature of reaction system remain on 40 ℃, stirring reaction is 10 hours under the condition of protection of inert gas;
(3) remove the solvent of reaction then under normal atmosphere, after the equal solvent normal hexane was all removed, the cut of 90-92 ℃/5 mmHg was collected in underpressure distillation, is four tert.-butoxy hafnium compounds.Product has passed through the evaluation of nucleus magnetic hydrogen spectrum.
1H?NMR?(300?MHz,?CDCl
3):?1.38?(s,?36H).
Embodiment 3:
The synthesis method of four tert.-butoxy hafniums, step is:
(1) under nitrogen atmosphere, add 49.2 gram potassium tert.-butoxide and 200 mL normal hexanes in the 500mL three-necked bottle, stir;
(2) will be by hafnium tetrachloride: potassium tert.-butoxide be that the hafnium tetrachloride of 1:4.8 mol ratio joins in the above-mentioned reaction system, and the temperature that keeps reaction system is at 60 ℃; After adding hafnium tetrachloride, allow the temperature of reaction system remain on 65 ℃, stirring reaction is 6 hours under the condition of protection of inert gas;
(3) remove the solvent of reaction then under normal atmosphere, after the equal solvent normal hexane was all removed, the cut of 90-92 ℃/5 mmHg was collected in underpressure distillation, is four tert.-butoxy hafnium compounds.Product has passed through the evaluation of nucleus magnetic hydrogen spectrum.
1H?NMR?(300?MHz,?CDCl
3):?1.38?(s,?36H).
Claims (1)
1. the synthesis method of four tert.-butoxy hafniums is characterized in that step is:
(1) under nitrogen atmosphere, the ratio in adding 100～400 ml n-hexanes in per 50 gram potassium tert.-butoxides adds potassium tert.-butoxide and normal hexane in the three-necked bottle, stir;
(2) by hafnium tetrachloride: potassium tert.-butoxide is the mol ratio of 1:4.4 ~ 1:4.8, and hafnium tetrachloride is joined in the above-mentioned reaction system, and the temperature that keeps reaction system is between 20 to 60 ℃; After adding hafnium tetrachloride, allow the temperature of reaction system remain between 40-65 ℃, under the condition of protection of inert gas stirring reaction 6-10 hour;
(3) remove the solvent of reaction then under normal atmosphere, after the equal solvent normal hexane was all removed, the cut of 90-92 ℃/5 mmHg was collected in underpressure distillation, is four tert.-butoxy hafnium compounds.
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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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|---|---|
| CN102351891A true CN102351891A (en) | 2012-02-15 |
| CN102351891B CN102351891B (en) | 2015-03-18 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601750A (en) * | 2013-10-28 | 2014-02-26 | 南京大学 | Tetrakis(ethylmethylamino)hafnium synthesis method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002274980A (en) * | 2001-03-22 | 2002-09-25 | Nagase Chemtex Corp | Ceramic tableware and method for manufacturing the same |
| JP2005209766A (en) * | 2004-01-21 | 2005-08-04 | Mitsubishi Materials Corp | Method for manufacturing oxide film containing hafnium |
| JP2007314437A (en) * | 2006-05-24 | 2007-12-06 | Adeka Corp | Organozirconium compound useful as precursor for forming thin film |
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2011
- 2011-08-31 CN CN201110254613.4A patent/CN102351891B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002274980A (en) * | 2001-03-22 | 2002-09-25 | Nagase Chemtex Corp | Ceramic tableware and method for manufacturing the same |
| JP2005209766A (en) * | 2004-01-21 | 2005-08-04 | Mitsubishi Materials Corp | Method for manufacturing oxide film containing hafnium |
| JP2007314437A (en) * | 2006-05-24 | 2007-12-06 | Adeka Corp | Organozirconium compound useful as precursor for forming thin film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601750A (en) * | 2013-10-28 | 2014-02-26 | 南京大学 | Tetrakis(ethylmethylamino)hafnium synthesis method |
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| CN102351891B (en) | 2015-03-18 |
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Granted publication date: 20150318 Termination date: 20210831 |