CN107118230A - Four（Dimethylamino）The synthetic method of germanium - Google Patents
Four（Dimethylamino）The synthetic method of germanium Download PDFInfo
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- CN107118230A CN107118230A CN201710492769.3A CN201710492769A CN107118230A CN 107118230 A CN107118230 A CN 107118230A CN 201710492769 A CN201710492769 A CN 201710492769A CN 107118230 A CN107118230 A CN 107118230A
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- China
- Prior art keywords
- dimethylamino
- germanium
- synthetic method
- added
- germanium according
- Prior art date
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 31
- 229910052732 germanium Inorganic materials 0.000 title description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title description 4
- YNYBCPCYMAHDCS-UHFFFAOYSA-N dimethylaminogermanium Chemical compound CN(C)[Ge] YNYBCPCYMAHDCS-UHFFFAOYSA-N 0.000 claims abstract description 36
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 7
- 150000002900 organolithium compounds Chemical class 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 4
- 150000002642 lithium compounds Chemical class 0.000 claims description 4
- YDGSUPBDGKOGQT-UHFFFAOYSA-N lithium;dimethylazanide Chemical compound [Li+].C[N-]C YDGSUPBDGKOGQT-UHFFFAOYSA-N 0.000 claims description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 3
- 125000001979 organolithium group Chemical group 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/30—Germanium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses the synthetic method of four (dimethylamino) germanium, first under inert atmosphere protection, dimethylamine and varsol are added in reactor, germanium tetrachloride is then added into system；Reaction is filtered and distilled after terminating, and obtains four (dimethylamino) germanium.Synthetic method of the present invention does not need any ether solvent, it is only necessary to single varsol, reduces the toxicity of synthesis cost and reaction, with more preferable operability, and yield is higher, contributes to the production of scale.
Description
Technical field
The present invention relates to a kind of synthetic method of four (dimethylamino) germanium.
Background technology
It is continuous as the MOS transistor size of its elemental device with continuing to develop for very large scale integration technology
Reduce, work as SiO2When the thickness of gate medium is reduced to nanometer scale, pass through SiO2Leakage current with thickness reduce exponentially increase,
So huge leakage current not only badly influences device performance, and ultimately results in SiO2Insulating effect can not be played.Use
High dielectric constant material substitutes SiO2It is the approach for being most hopeful to solve this problem at present.
Semiconductor manufacturing industry is continued to develop so that have to look for being adapted to high K and the metal gate material that ALD and CVD is used
Presoma.For 32nm technology nodes, the volatility of material becomes most important the problems such as transfer ways and purity.
As information is stored and amount to obtain is substantially improved, the demand for more high-k material also constantly heats up.The appropriate high K of selection
Material, can meet the requirement in the productions such as dielectric constant, thermodynamic stability, gate electrode compatibility and boundary layer stability.
Four (dimethylamino) germanium compounds are developed exactly to carry out for the purposes of high K presomas above.Four (diformazan ammonia
Base) it is liquid under germanium normal temperature, it is the compound very sensitive to air and steam, hydro carbons, carbon tetrachloride etc. can be dissolved in organic molten
In agent, not only with preferable stability, higher vapour pressure, and at a relatively high reactivity is shown, be that ALD is ground now
Study carefully the focus in field.
Current domestic report also not on four (dimethylamino) germanium synthetic methods.
The content of the invention
The purpose of the present invention be overcome the shortcomings of prior art exist there is provided one kind four (dimethylamino) germanium synthesis side
Method.
The purpose of the present invention is achieved through the following technical solutions：
The synthetic method of four (dimethylamino) germanium, feature is：Comprise the following steps：
1) under inert atmosphere protection, dimethylamine and varsol are added in the reactor, then being added into system has
Machine lithium compound, is made dimethylamino lithium；
2) germanium tetrachloride is added into system；
3) reaction is filtered and distilled after terminating, and obtains four (dimethylamino) germanium.
Further, the synthetic method of four above-mentioned (dimethylamino) germanium, wherein, the organo-lithium compound is normal-butyl
Lithium.
Further, the synthetic method of four above-mentioned (dimethylamino) germanium, wherein, the dimethylamine and organo-lithium compound
Consumption mol ratio be 1~1.2:1.
Further, the synthetic method of four above-mentioned (dimethylamino) germanium, wherein, the organo-lithium compound and four chlorinations
The consumption mol ratio of germanium is 4~4.2:1.
Further, the synthetic method of four above-mentioned (dimethylamino) germanium, wherein, step 1), in -10~10 DEG C of temperature
Under the conditions of react 6~10 hours.
Further, the synthetic method of four above-mentioned (dimethylamino) germanium, wherein, step 2), in -30~10 DEG C of temperature
Under the conditions of react 8~12 hours.
Further, the synthetic method of four above-mentioned (dimethylamino) germanium, wherein, the distillation technique collects 30~100
DEG C/1mmHg cut.
Further, the synthetic method of four above-mentioned (dimethylamino) germanium, wherein, the varsol is n-hexane.
Further, the synthetic method of four above-mentioned (dimethylamino) germanium, wherein, the inert atmosphere is nitrogen atmosphere.
Further, the synthetic method of four above-mentioned (dimethylamino) germanium, wherein, step 1), it is added dropwise while stirring organic
Lithium compound.
Further, the synthetic method of four above-mentioned (dimethylamino) germanium, wherein, step 3), first air-distillation goes out solvent,
Vacuum distillation again, collects the cut steamed.
The present invention has significant advantage and beneficial effect compared with prior art, embodies in the following areas：
The synthetic method of four (dimethylamino) germanium of the invention, first under inert atmosphere protection, adds diformazan in reactor
Amine and varsol, then add germanium tetrachloride into system；Reaction is filtered and distilled after terminating, and obtains four (diformazans
Amino) germanium.Synthetic method of the present invention does not need any ether solvent, it is only necessary to single varsol, reduces synthesis cost
With the toxicity of reaction, with more preferable operability, and yield is higher, contributes to the production of scale.
Embodiment
In order to which technical characteristic, purpose and effect to the present invention are more clearly understood from, specific implementation is now described in detail
Scheme.
The specific synthesis technique of four (dimethylamino) germanium is：
1) under inert atmosphere protection, dimethylamine and varsol are added in the reactor, then being added into system has
Machine lithium compound, reacts 6~10 hours under -10~10 DEG C of temperature conditionss, and dimethylamino lithium is made；Dimethylamine and organic lithiumation
The consumption mol ratio of compound is 1~1.2:1；Inert atmosphere is nitrogen atmosphere, and varsol is n-hexane, and organo-lithium compound is
N-BuLi；
2) germanium tetrachloride is added into system, is reacted 8~12 hours under -30~10 DEG C of temperature conditionss；Organolithium chemical combination
The consumption mol ratio of thing and germanium tetrachloride is 4~4.2:1；
3) reaction is filtered and distilled after terminating, and first air-distillation goes out solvent, then vacuum distillation, and what collection was steamed evaporates
Point, distillation technique collects 30~100 DEG C/1mmHg cut；Obtain four (dimethylamino) germanium.
Embodiment 1
Under inert atmosphere, 90g dimethylamine, 300mL n-hexanes are added in 2L reaction bulb, system temperature is kept -10
~10 DEG C or so, 2.5mol/L n-BuLi hexane solution 500mL, completion of dropping, after being warmed to room temperature are added dropwise while stirring
Maintain stirring 4 hours.
66g germanium tetrachlorides are added dropwise in above-mentioned reaction system, temperature of reaction system are kept at -30~10 DEG C or so, drop
Add after finishing, after being warmed to room temperature, maintenance system temperature is not less than 60 DEG C and is heated to reflux 4 hours under inert gas shielding.
After reaction terminates, system is filtered, and then progress air-distillation is gone out solvent, then vacuum distillation, and what is steamed evaporates
Divide, as target compound four (dimethylamino) germanium, obtain product 65g, yield 85%, product has passed through the mirror of nucleus magnetic hydrogen spectrum
It is fixed.
Embodiment 2
Under inert atmosphere, 300g dimethylamine, 1000mL n-hexanes are added in 5L reaction bulb, keep system temperature-
10~10 DEG C or so, 2.5mol/L n-BuLi hexane solution 1500mL is added dropwise while stirring, completion of dropping is warmed to room temperature
Stirring 4 hours is maintained afterwards.
198g germanium tetrachlorides are added dropwise in above-mentioned reaction system, temperature of reaction system are kept at -30~10 DEG C or so,
After completion of dropping, after being warmed to room temperature, maintenance system temperature is not less than 60 DEG C and is heated to reflux 4 hours under inert gas shielding.
After reaction terminates, system is filtered, and then progress air-distillation is gone out solvent, then vacuum distillation, and what is steamed evaporates
Divide, as target compound four (dimethylamino) germanium, obtain product 183g, yield 80%, product has passed through the mirror of nucleus magnetic hydrogen spectrum
It is fixed.
In summary, synthetic method of the present invention does not need any ether solvent, it is only necessary to single varsol,
The toxicity of synthesis cost and reaction is reduced, with more preferable operability, and yield is higher, contributes to the production of scale.
It should be noted that：The preferred embodiment of the present invention is the foregoing is only, the power of the present invention is not limited to
Sharp scope；Simultaneously more than description, should can understand and implement for the special personage of correlative technology field, thus it is other without departing from
The equivalent change or modification completed under disclosed spirit, should be included in claim.
Claims (11)
1. the synthetic method of four (dimethylamino) germanium, it is characterised in that：Comprise the following steps：
1) under inert atmosphere protection, dimethylamine and varsol are added in the reactor, organolithium is then added into system
Compound, is made dimethylamino lithium；
2) germanium tetrachloride is added into system；
3) reaction is filtered and distilled after terminating, and obtains four (dimethylamino) germanium.
2. the synthetic method of four (dimethylamino) germanium according to claim 1, it is characterised in that：The organo-lithium compound
For n-BuLi.
3. the synthetic method of four (dimethylamino) germanium according to claim 1, it is characterised in that：The dimethylamine with it is organic
The consumption mol ratio of lithium compound is 1~1.2:1.
4. the synthetic method of four (dimethylamino) germanium according to claim 1, it is characterised in that：The organo-lithium compound
Consumption mol ratio with germanium tetrachloride is 4~4.2:1.
5. the synthetic method of four (dimethylamino) germanium according to claim 1, it is characterised in that：Step 1), -10~10
Reacted 6~10 hours under DEG C temperature conditionss.
6. the synthetic method of four (dimethylamino) germanium according to claim 1, it is characterised in that：Step 2), -30~10
Reacted 8~12 hours under DEG C temperature conditionss.
7. the synthetic method of four (dimethylamino) germanium according to claim 1, it is characterised in that：The distillation technique is collected
30~100 DEG C/1mmHg cut.
8. the synthetic method of four (dimethylamino) germanium according to claim 1, it is characterised in that：The varsol is just
Hexane.
9. the synthetic method of four (dimethylamino) germanium according to claim 1, it is characterised in that：The inert atmosphere is nitrogen
Gas atmosphere.
10. the synthetic method of four (dimethylamino) germanium according to claim 1, it is characterised in that：Step 1), while stirring
Organo-lithium compound is added dropwise.
11. the synthetic method of four (dimethylamino) germanium according to claim 1, it is characterised in that：Step 3), first normal pressure steams
Solvent, then vacuum distillation are distillated, the cut steamed is collected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710492769.3A CN107118230A (en) | 2017-06-26 | 2017-06-26 | Four（Dimethylamino）The synthetic method of germanium |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710492769.3A CN107118230A (en) | 2017-06-26 | 2017-06-26 | Four（Dimethylamino）The synthetic method of germanium |
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| Publication Number | Publication Date |
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| CN107118230A true CN107118230A (en) | 2017-09-01 |
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| CN201710492769.3A Pending CN107118230A (en) | 2017-06-26 | 2017-06-26 | Four（Dimethylamino）The synthetic method of germanium |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999257A (en) * | 2021-11-26 | 2022-02-01 | 江苏南大光电材料股份有限公司 | Preparation method of semiconductor grade tetra (methylethylamino) zirconium |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5344948A (en) * | 1992-02-25 | 1994-09-06 | Iowa State University Research Foundation, Inc. | Single-source molecular organic chemical vapor deposition agents and use |
| US20060138393A1 (en) * | 2004-12-27 | 2006-06-29 | Samsung Electronics Co., Ltd. | Ge precursor, GST thin layer formed using the same, phase-change memory device including the GST thin layer, and method of manufacturing the GST thin layer |
| KR20150097429A (en) * | 2014-02-17 | 2015-08-26 | 주식회사 유진테크 머티리얼즈 | Precursor compositions for forming germanium antimony telurium alloy and method of forming germanium antimony telurium alloy layer using them as precursors |
| CN106103456A (en) * | 2014-03-18 | 2016-11-09 | 株式会社Eugene科技材料 | Organic germanium amines and the method with its deposition thin film |
-
2017
- 2017-06-26 CN CN201710492769.3A patent/CN107118230A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5344948A (en) * | 1992-02-25 | 1994-09-06 | Iowa State University Research Foundation, Inc. | Single-source molecular organic chemical vapor deposition agents and use |
| US20060138393A1 (en) * | 2004-12-27 | 2006-06-29 | Samsung Electronics Co., Ltd. | Ge precursor, GST thin layer formed using the same, phase-change memory device including the GST thin layer, and method of manufacturing the GST thin layer |
| KR20150097429A (en) * | 2014-02-17 | 2015-08-26 | 주식회사 유진테크 머티리얼즈 | Precursor compositions for forming germanium antimony telurium alloy and method of forming germanium antimony telurium alloy layer using them as precursors |
| CN106103456A (en) * | 2014-03-18 | 2016-11-09 | 株式会社Eugene科技材料 | Organic germanium amines and the method with its deposition thin film |
Non-Patent Citations (2)
| Title |
|---|
| HERBERT H. ANDERSON，: "Dialkylaminogermanes and dialkylaminosilanes", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| YANJIAN WANG等，: "Synthesis and Interconversions of Azagermatranes", 《INORG. CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999257A (en) * | 2021-11-26 | 2022-02-01 | 江苏南大光电材料股份有限公司 | Preparation method of semiconductor grade tetra (methylethylamino) zirconium |
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Application publication date: 20170901 |