CN108218907A - A kind of high-purity double diethylin device for preparing silane and method - Google Patents
A kind of high-purity double diethylin device for preparing silane and method Download PDFInfo
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- CN108218907A CN108218907A CN201810235838.7A CN201810235838A CN108218907A CN 108218907 A CN108218907 A CN 108218907A CN 201810235838 A CN201810235838 A CN 201810235838A CN 108218907 A CN108218907 A CN 108218907A
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- Prior art keywords
- reactor
- silane
- diethylin
- condenser
- receiver
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- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 title claims abstract description 17
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title abstract description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims abstract description 13
- OWKFQWAGPHVFRF-UHFFFAOYSA-N n-(diethylaminosilyl)-n-ethylethanamine Chemical compound CCN(CC)[SiH2]N(CC)CC OWKFQWAGPHVFRF-UHFFFAOYSA-N 0.000 claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- JBJKCFKLTPROGT-UHFFFAOYSA-N CCCCCCCCCCCC.Cl[SiH2]Cl Chemical compound CCCCCCCCCCCC.Cl[SiH2]Cl JBJKCFKLTPROGT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 4
- 238000006073 displacement reaction Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000011541 reaction mixture Substances 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000003039 volatile agent Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LXXSWZYRKAQQDI-UHFFFAOYSA-N n-ethyl-n-silylethanamine Chemical compound CCN([SiH3])CC LXXSWZYRKAQQDI-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- -1 reactor 2 Chemical compound 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method 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
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a kind of high-purity double diethylin device for preparing silane and methods, device includes reactor, reactor head is equipped with feeder and condenser, condenser bottom connects filter top, filter bottom connects rectifying tower reactor, rectifying tower reactor top connects rectifying column, and receiver A and receiver B is connected at the top of rectifying column.Preparation method is to be passed through inert gas argon gas by condenser pipe in condenser to carry out reactor heating evacuation displacement, by dodecane, triethylamine and diethylamine are added in reactor, dichlorosilane dodecane solution is added in feeder, 0 DEG C of degree left and right of temperature of reactor is kept, after completion of dropwise addition, reaction mixture temperature rise reaches room temperature, continue stirring 3 hours, reaction is completed.The present invention can prepare bis- (diethylamino) silane, and impurity index reaches electron level requirement, and reliable raw material is provided for silica and the high K thin film growth of silicon systems.
Description
Technical field
The present invention relates to a kind of high-purity double diethylin silane to prepare purifying technique, relates particularly to a kind of dichloro-dihydro
Silicon and diethylamine reaction, using triethylamine and dodecane as solvent, form target product.High pure electronic grade is obtained by synthesizing and purifying
High-purity double diethylin silane process, belong to chemical industry synthesis separation technology field.
Background technology
High-purity bis- (diethylamino) silane are semiconductor technology main raw material(s)s.It mainly applies in low temperature atomic layer gas
Mutually deposition (ALD) technology prepares the novel organic source of silica, while be used to prepare the new material of the high K films of silicon systems.The material
Material be a major advantage that under high volatile, wide scope temperature condition Self-limiting growth characteristic, reduce film carbon and stain, easily
The relatively low material consumption of the film and growth course of formation constant composition and property.In recent years, with the fast of semiconductor technology
Speed progress, growth technique cause to the demand of the series of products such as high-purity bis- (diethylamino) silane for ALD techniques to former material
The metals content impurity control of material has certain requirement, can be with using high-purity bis- (diethylamino) silane of purity 99.999%
Ensure that the electric conductivity efficiency of growth material meets technology requirement.The impurity wherein mainly controlled includes Fe, Zn, Si, Cu, Al, Ge
Deng.
(diethylamino) silane bis- in order to obtain, can select different synthetic methods to prepare, obtain the high-purity of crude product
Bis- (diethylamino) silane by rectification and purification, obtain high-purity bis- (diethylamino) silane products.
Invention content
The object of the present invention is to provide a kind of high-purity bis- (diethylamino) silane synthesis purifying technique processes, the technique packets
Processes, high-purity bis- (diethylamino) silane purity such as Material synthesis part, rectifying part, analysis detection are included to reach
99.999%, impurity index to electron level requirement.
The present invention provides a kind of high-purity double diethylin silane preparation methods, and indifferent gas is passed through by condenser pipe in condenser
Body argon gas carries out reactor heating and evacuates displacement, and by dodecane, triethylamine and diethylamine are added in reactor, dichlorosilane
Dodecane solution is added in feeder addition funnel, and feed time maintains 60-80 minutes, and reactor is kept using mixture of ice and water
0 DEG C of degree left and right of temperature, after completion of dropwise addition, reaction mixture temperature rise reaches room temperature, continues stirring 3 hours, and reaction is completed.Its
In, dodecane, triethylamine, diethylamine, 0.177g/ml dichlorosilane dodecane solution usage ratio be：500ml：160ml：
100ml：200ml.
The reaction generates a large amount of triithylamine base hydrochlorides and diethylin hydrochloride.In order to ensure forming fine grained salt, no
Influence continuously stirs effect, and raw material dropwise addition carries out stage by stage, and half an hour is added dropwise in leading portion, stops being added dropwise intermittently being added dropwise again after ten minutes
The other half.
The method of being further processed is to be filtered material in reactor by filter, realizes separation of solid and liquid, is removed solid
Body salt.It collects filtrate and carries out rectifying separation, select diameter 20*500mm rectifying columns in rectifying column, add 2mm quartz ring fillers,
Control reflux ratio 2:1, front-end volatiles and tails are collected using receiver A and receiver B, take stable 93 DEG C of degree of intermediate products boiling point
For bis- (diethylamino) silane.It obtains bis- (diethylamino) silane and reaches 70% with dichlorosilane rate of collecting.
The present invention provides a kind of high-purity double diethylin device for preparing silane, and including reactor 2,2 top of reactor is equipped with
Feeder 1 and condenser 3,3 bottom of condenser connection filter, 4 top, 4 bottom of filter connection rectifying tower reactor 5, rectifying tower reactor
5 tops connect rectifying column 6,6 top connection receiver A7 and receiver B8 of rectifying column.
Further, in the above-mentioned technical solutions, agitating device is equipped in reactor 2.
Further, in the above-mentioned technical solutions, 2mm quartz ring fillers are used in rectifying column 6.
Description of the drawings
Fig. 1 is apparatus of the present invention structure diagram；
In figure, 1, feeder；2nd, reactor；3rd, condenser；4th, filter；5th, rectifying tower reactor；6th, rectifying column；7th, receiver
A；8th, receiver B.
Specific embodiment
Following nonlimiting examples can make those of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Embodiment 1
A kind of high-purity double diethylin device for preparing silane, including reactor 2,2 top of reactor is equipped with feeder 1 and cold
Condenser 3,3 bottom of condenser connection filter, 4 top, 4 bottom of filter connection rectifying tower reactor 5,5 top of rectifying tower reactor connection essence
Evaporate tower 6,6 top connection receiver A7 and receiver B8 of rectifying column.
Agitating device is equipped in reactor 2.
2mm quartz ring fillers are used in rectifying column 6.
A kind of high-purity double diethylin silane preparation methods, inert gas argon gas is passed through to anti-by condenser pipe in condenser
Device is answered to carry out heating and evacuates displacement, by 500ml dodecanes, triethylamine (116.15g, 1.15moles, 160ml) and diethylamine
(69.36g, 0.95moles, 100ml) is added in reaction bulb feeder, dichlorosilane dodecane solution (35.4g,
0.35moles, 200ml) it adds in addition funnel, feed time maintains 60-80 minutes, and mixture of ice and water keeps temperature of reactor
0 DEG C of degree left and right, after completion of dropwise addition, reaction mixture temperature rise reaches room temperature, continues stirring 3 hours, and reaction is completed.
The reaction generates a large amount of triithylamine base hydrochlorides and diethylin hydrochloride.In order to ensure forming fine grained salt, no
Influence continuously stirs effect, and raw material dropwise addition carries out stage by stage, and half an hour is added dropwise in leading portion, stops being added dropwise intermittently being added dropwise again after ten minutes
The other half.
Material in reactor by filter is filtered, realizes separation of solid and liquid, removes solid salt.Collect filtrate into
Row rectifying detaches, and diameter 20*500mm rectifying columns are selected in rectifying column, adds 2mm quartz ring fillers, controls reflux ratio 2:1, it adopts
Front-end volatiles and tails are collected with receiver A and receiver B, it is bis- (diethylaminos) to take stable 93 DEG C of degree of intermediate products boiling point
Silane.It obtains bis- (diethylamino) silane and reaches 70% with dichlorosilane rate of collecting.
The present invention can prepare bis- (diethylamino) silane, and impurity index reaches electron level requirement, be silica and silicon systems
High K thin film growth provides reliable raw material.Product carry out impurity analysis, analytical instrument use ICP-MS, Fe, Mg, Mn, Na, Ni,
Ca, Zn, Si, Cu, Al, Ge impurity content summation are less than 100ppb.
Claims (6)
1. a kind of high-purity double diethylin device for preparing silane, it is characterised in that：Including reactor, reactor head is equipped with charging
Device and condenser, condenser bottom connection filter top, filter bottom connection rectifying tower reactor, rectifying tower reactor top connection essence
Tower is evaporated, receiver A and receiver B is connected at the top of rectifying column.
2. high-purity double diethylin device for preparing silane according to claim 1, it is characterised in that：Stirring is equipped in reactor
Device.
3. high-purity double diethylin device for preparing silane according to claim 1, it is characterised in that：2mm is used in rectifying column
Quartzy ring filler.
4. a kind of high-purity double diethylin silane preparation methods, it is characterised in that：
Inert gas argon gas is passed through by condenser pipe in condenser, heating evacuation displacement is carried out to reactor, by dodecane, three second
Amine and diethylamine are added in reactor, and dichlorosilane dodecane solution is added in feeder, and feed time maintains 60-80 points
Clock keeps 0 DEG C of degree left and right of temperature of reactor, and after completion of dropwise addition, reaction mixture temperature rise reaches room temperature, and it is small to continue stirring 3
When, reaction is completed；
Material in reactor by filter is filtered, filtrate is collected and carries out rectifying separation, diameter 20* is selected in rectifying column
500mm rectifying columns control reflux ratio 2:1, front-end volatiles and tails are collected using receiver A and receiver B, takes and stablizes intermediate produce
93 DEG C of degree of product boiling point are bis- (diethylamino) silane.
5. high-purity double diethylin silane preparation methods according to claim 4, it is characterised in that：
Wherein, dodecane, triethylamine, diethylamine, 0.177g/ml dichlorosilane dodecane solution usage ratio be：500ml：
160ml：100ml：200ml.
6. high-purity double diethylin silane preparation methods according to claim 4, it is characterised in that：
Raw material dropwise addition carries out stage by stage, and half an hour is added dropwise in leading portion, stops being added dropwise that the other half being intermittently added dropwise again after ten minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810235838.7A CN108218907A (en) | 2018-03-21 | 2018-03-21 | A kind of high-purity double diethylin device for preparing silane and method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810235838.7A CN108218907A (en) | 2018-03-21 | 2018-03-21 | A kind of high-purity double diethylin device for preparing silane and method |
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| Publication Number | Publication Date |
|---|---|
| CN108218907A true CN108218907A (en) | 2018-06-29 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430245A (en) * | 2020-11-24 | 2021-03-02 | 江西晨光新材料股份有限公司 | Synthesis system and synthesis method of silicon nitrogen heterocyclic aminosilane |
| CN112661781A (en) * | 2020-12-26 | 2021-04-16 | 浙江博瑞电子科技有限公司 | Preparation method of bis (tert-butylamino) silane |
| CN114573628A (en) * | 2022-04-13 | 2022-06-03 | 洛阳中硅高科技有限公司 | System and method for preparing amino silane |
| CN116036630A (en) * | 2023-01-10 | 2023-05-02 | 贵州威顿晶磷电子材料股份有限公司 | Manufacturing device and manufacturing method of electronic-grade bis-diethylamino-silane |
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| CN105837611A (en) * | 2015-01-13 | 2016-08-10 | 苏州复纳电子科技有限公司 | Preparation method of di(diethylamino)silane |
| KR20160144550A (en) * | 2015-06-08 | 2016-12-19 | 주식회사 케이씨씨 | Method for removing compounds having Si-O bond from aminosilanes |
| CN107406466A (en) * | 2015-03-24 | 2017-11-28 | 捷恩智株式会社 | The manufacture method of dialkyl amino base silane |
| CN107629084A (en) * | 2017-09-28 | 2018-01-26 | 荆州市江汉精细化工有限公司 | One kind two（Lignocaine）Methoxy methyl base silane synthesis technique is invented |
-
2018
- 2018-03-21 CN CN201810235838.7A patent/CN108218907A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105837611A (en) * | 2015-01-13 | 2016-08-10 | 苏州复纳电子科技有限公司 | Preparation method of di(diethylamino)silane |
| CN107406466A (en) * | 2015-03-24 | 2017-11-28 | 捷恩智株式会社 | The manufacture method of dialkyl amino base silane |
| KR20160144550A (en) * | 2015-06-08 | 2016-12-19 | 주식회사 케이씨씨 | Method for removing compounds having Si-O bond from aminosilanes |
| CN107629084A (en) * | 2017-09-28 | 2018-01-26 | 荆州市江汉精细化工有限公司 | One kind two（Lignocaine）Methoxy methyl base silane synthesis technique is invented |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430245A (en) * | 2020-11-24 | 2021-03-02 | 江西晨光新材料股份有限公司 | Synthesis system and synthesis method of silicon nitrogen heterocyclic aminosilane |
| CN112430245B (en) * | 2020-11-24 | 2023-03-03 | 江西晨光新材料股份有限公司 | Synthesis system and synthesis method of silicon nitrogen heterocyclic aminosilane |
| CN112661781A (en) * | 2020-12-26 | 2021-04-16 | 浙江博瑞电子科技有限公司 | Preparation method of bis (tert-butylamino) silane |
| CN114573628A (en) * | 2022-04-13 | 2022-06-03 | 洛阳中硅高科技有限公司 | System and method for preparing amino silane |
| CN116036630A (en) * | 2023-01-10 | 2023-05-02 | 贵州威顿晶磷电子材料股份有限公司 | Manufacturing device and manufacturing method of electronic-grade bis-diethylamino-silane |
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