CN108862282A - The preparation method of disilane - Google Patents
The preparation method of disilane Download PDFInfo
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- CN108862282A CN108862282A CN201810903987.6A CN201810903987A CN108862282A CN 108862282 A CN108862282 A CN 108862282A CN 201810903987 A CN201810903987 A CN 201810903987A CN 108862282 A CN108862282 A CN 108862282A
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- disilane
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/04—Hydrides of silicon
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Abstract
An embodiment of the present invention provides a kind of preparation method of disilane, includes the following steps：The chloro disilane by-product that improved Siemens generate is provided；The by-product is filtered, filtrate is obtained；By the filtrate by rectification process, the refined solution of chloro disilane is obtained；And chloro disilane in the refined solution is restored, the disilane is made.The preparation method of an embodiment of the present invention prepares the high-purity disilane for meeting semicon industry application by being recycled, being refined to the chloro disilane in improved Siemens polysilicon production process.
Description
Technical field
The present invention relates to the preparation methods of disilane, specially a kind of to prepare the high-purity second for meeting semicon industry application
The preparation method of silane.
Background technique
Disilane is mainly used for the side such as solar battery, photosensitive rotating cylinder, amorphous silicon film, epitaxial growth, chemical vapor deposition
Face.When as sedimentary origin, sedimentary is silicon oxide or silicon nitride, compared with silane, disilane have deposition velocity faster, deposition
The lower feature of temperature can prevent from generating ball bumps in unformed silicon, can be improved the homogeneity being deposited into, be mainly used in
The manufacture of 20 nanometers or less high-end chips.
It is more faster in the deposition velocity of amorphous silicon on piece than with silane with disilane in manufacture of solar cells, and temperature
Degree can reduce by 200~300 DEG C；In ion implanting, easily build-up of luminance, line is strong after making ion source with disilane, and effect is significantly better than
Make ion source with other gases；It is used for extension and diffusion technique in semiconductor processing, is also used for solar battery and electronics shines
Photosensitive drums mutually；When using disilane, expensive quartz glass can be replaced to make the base of LCD using the lower glass of price
Material.
Currently, the preparation of disilane mainly has chloro disilane reduction method and magnesium silicide to react two kinds of sides of synthesis with ammonium chloride
Method.Wherein, chloro disilane reduction method is the complex metal hydrides deoxygenization chlorination disilane alkane such as lithium aluminium hydride reduction or sodium aluminum hydride
Disilane is prepared, but in this method, chloro disilane needs to carry out separately synthesized, and synthesis difficulty is big and low yield.
And magnesium silicide is that magnesium silicide carries out reacting generation disilane with ammonium chloride, but produces in the process with ammonium chloride reaction method
Product are mainly silane, and disilane accounting is to be recycled as by-product, therefore main pass through controls pair only 3% or so
The yield of product improves disilane yield, limits the feasibility that this method produces disilane as major product.Separately
Outside, magnesium silicide is reacted with ammonium chloride can generate solid magnesium chloride hexammoniate, in view of the higher risk of disilane, the technology of this method
Difficult point is mainly：1, how disilane and silane are separated；2, how from the waste residue of silane reaction kettle separating-purifying second
Silane.
Summary of the invention
A primary object of the present invention is providing a kind of preparation method of disilane, includes the following steps：Improvement is provided
The chloro disilane by-product that Siemens Method generates；The by-product is filtered, filtrate is obtained；The filtrate is passed through into essence
Processing is evaporated, the refined solution of chloro disilane is obtained；And chloro disilane in the refined solution is restored, the second silicon is made
Alkane.
According to an embodiment of the present invention, the rectification process includes the first rectification process and the second rectification process.
According to an embodiment of the present invention, first rectification process carries out in first rectifying column, second rectifying
Processing carries out in Second distillation column.
According to an embodiment of the present invention, the tower top pressure of the first rectifying column is 50~120KPa, and tower top temperature is
90~130 DEG C, plate theory series is 60~120.
According to an embodiment of the present invention, the tower top pressure of the Second distillation column is 40~100KPa, and tower top temperature is
90~110 DEG C, plate theory series is 70~90.
According to an embodiment of the present invention, pass through lithium aluminium hydride reduction, sodium aluminum hydride or diethylaluminum hydride and the chloro second
Disilane is made in the reduction reaction of silane.
According to an embodiment of the present invention, the method also includes reacting resulting disilane to pass through at third rectifying
Reason, the 4th rectification process and the 5th rectification process are purified.
According to an embodiment of the present invention, the third rectification process carries out in third distillation column, the 4th rectifying
Processing carries out in the 4th rectifying column, and the 5th rectification process carries out in the 5th rectifying column, and the third distillation column passes through
Tower top is connected with the 4th rectifying column, and the 4th rectifying column is connected by tower bottom with the 5th rectifying column.
According to an embodiment of the present invention, the tower top temperature of the third distillation column is -10~10 DEG C, the 4th rectifying
The tower top temperature of tower is -50~-30 DEG C, and the tower top temperature of the 5th rectifying column is -20~-15 DEG C.
According to an embodiment of the present invention, the method includes passing through molecular sieve and/or active carbon to the resulting second of reaction
Silane carries out adsorption treatment.
The preparation method of an embodiment of the present invention, by the chloro second in improved Siemens polysilicon production process
Silane is recycled, is refined, and the high-purity disilane for meeting semicon industry application is prepared.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of the disilane of an embodiment of the present invention；
Fig. 2 is the structural schematic diagram of the device for preparing disilane of an embodiment of the present invention.
Specific embodiment
The exemplary embodiment for embodying feature of present invention and advantage will describe in detail in the following description.It should be understood that
The present invention can have various variations in different embodiments, neither depart from the scope of the present invention, and theory therein
Bright and diagram inherently is illustrated as being used, rather than to limit the present invention.
In improved Siemens polysilicon production process, a small amount of chloro second silicon can be generated in reduction process and hydrogenation process
Alkane, chloro disilane are a silicon hexachloride, two silicon hexachlorides, trichloroethyl silane, four silicon hexachlorides, five silicon hexachlorides and hexachloroethanc
The mixture of silane, above-mentioned chloro disilane is enriched in polysilicon raffinate after concentration.An embodiment of the present invention passes through
Polysilicon raffinate is handled, chloro disilane therein is recycled and refined, obtains high-purity chloro disilane, and with
This prepares disilane by reduction reaction for raw material.
An embodiment of the present invention provides a kind of preparation method of disilane, includes the following steps：
The chloro disilane by-product (polysilicon raffinate) that improved Siemens generate is provided；
By-product is filtered, filtrate is obtained；
By filtrate by rectification process, the refined solution of chloro disilane is obtained；And
The chloro disilane in refined solution is restored, disilane is made.
As shown in Figure 1, the preparation method of the disilane of an embodiment of the present invention, it may include filtering, the first rectification process,
Second rectification process, deoxygenization chlorination disilane, third rectification process, the 4th rectification process, the 5th rectification process, active carbon are inhaled
Attached, molecular sieve absorption and etc..
In an embodiment, polysilicon raffinate is filtered, can remove solid impurity, the solid impurity for example comprising
Particulate material, metal-containing polymer, impurity containing amorphous silicon and metal etc..
In an embodiment, the removal rate of solid impurity in filtration step, filtering can be controlled by adjusting filtering accuracy
Precision is preferably 0.5~1 μm.Filtering accuracy control can farthest be removed containing amorphous silicon and gold within the above range
The impurity of category, filtering accuracy is too small, and filter is easy blocking to frequently overhaul, and the excessive then removal rate of filtering accuracy reduces.
In an embodiment, the high-boiling-point impurity in filtrate can be removed by the first rectification process step, passes through second
Rectification process step removes the low boiling impurity in filtrate.
In an embodiment, high-boiling-point impurity includes methylchlorosilane, chloro disilane and gold in polysilicon raffinate
Belong to high polymer, low boiling impurity includes the chlorosilanes such as low-boiling-point substance, such as trichlorosilane, silicon tetrachloride.
In an embodiment, pass through complex metal hydride, such as lithium aluminium hydride reduction, sodium aluminum hydride, diethylaluminum hydride
Deoxygenization chlorination disilane prepares disilane.Specific reaction equation for example can be：
LiAlH4+Si2HmCln-Si2H6+LiCl+AlCl3(m+n=6)
Wherein, by-product silane has been supervened in reaction process.
Above-mentioned reduction reaction carries out in a solvent, and solvent can be ether and/or tetrahydrofuran.Due to the metal in reaction
The activity of hydride and chloro disilane is very high, vigorous reaction can occur with water, therefore solvent is removed water, at deoxygenation
Reason adds reaction system to guarantee reaction required anhydrous and oxygen-free environment after the completion of processing.
In an embodiment, removed water by the way that the metals such as lithium metal, sodium are added into reaction dissolvent, deoxygenation.
In an embodiment, the step of deoxygenization chlorination disilane, may include：By lithium aluminium hydride reduction, sodium aluminum hydride or diethyl
The complex metal hydrides such as aluminum hydride are dissolved in ether or tetrahydrofuran solvent, controlled at -20~20 DEG C, and using lazy
Property gas is protected；Later, the mixture of complex metal hydride and solvent is added in chloro disilane and is reacted.
In reduction reaction, the order of addition of reactant has apparent influence to product, and chlorine is added in complex metal hydride
For in disilane, the disilane content of product is higher, is more advantageous to the generation of disilane；After sequence is inverted, silane contents increase,
Disilane content is reduced.
In an embodiment, when the mole dosage of chloro disilane is 2~5 times of complex metal hydride, reaction turns
Rate is optimal.
In an embodiment, the mole dosage of reaction dissolvent is 2~8 times of complex metal hydride.
In an embodiment, protective gas can be nitrogen, argon gas, helium, preferably helium.
In an embodiment, complex metal hydride and chloro disilane reaction products therefrom are carried out at third rectifying
The purification steps such as reason, the 4th rectification process, the 5th rectification process obtain the high-purity disilane for meeting semicon industry application.
Wherein, remaining reaction dissolvent, chloro disilane etc. are removed by third rectification process；Pass through the 4th rectification process
Remove the low-boiling by-products that the boiling points such as silane, hydrogen, hydrogen chloride are lower than -50~-30 DEG C；Dechlorination is removed by the 5th rectification process
It is lower than -20~-15 DEG C of low-boiling by-products for boiling points such as disilane, silane, hydrogen chloride.
It further include being inhaled by molecular sieve and/or active carbon to the disilane of rectifying after purification in an embodiment
Attached processing purifies disilane by the method for rectifying Joint adsorption.
In an embodiment, product is first handled through activated carbon adsorption, then through molecular sieve adsorption treatment.
In an embodiment, active carbon can further remove B, P in disilane, Al, Fe, etc. metals and nonmetallic
Impurity, product purity reach 5N, O2≤ 1.0, N2≤ 2.0, H2O≤1.0, SiH4≤ 400, CO2≤ 1.0, CH4≤1.0(ppmv)。
In an embodiment, molecular sieve can be 4A, 4.5A, 5A molecular sieve or their mixture；Active carbon can be with
To be spherical or cylindrical, iodine sorption value with higher and specific surface area, the specific surface area of active carbon can be 400~800m2/
G, iodine sorption value >=1100mg/g.
In an embodiment, active carbon and molecular sieve are pre-processed, to remove moisture removal.It such as can be at dry
Reason, drying temperature can be 90~200 DEG C, to prevent high-temp combustion, be dried under an inert atmosphere, inert gas can be
Nitrogen, argon gas or helium.
In an embodiment, the ratio of height to diameter of adsorption column is between 2~9, and adsorption temp is between -35~20 DEG C, absorption
Column wall does electrobrightening processing.
It is carried out in the device that the preparation of the disilane of an embodiment of the present invention can be shown in Fig. 2, which includes impurity
Collector 40, and the filter element 10, first rectifying column 21, Second distillation column 22, the reactor 30, third rectifying that are sequentially communicated
Tower 23, the 4th rectifying column 24, the 5th rectifying column 25, absorber 31 and absorber 32.
When operation, polysilicon raffinate enters filter element 10 and is filtered, and gained filtrate enters the progress of first rectifying column 21
First rectification process, the high-boiling-point impurity in filtrate stay in the tower reactor of first rectifying column 21, the steam comprising chloro disilane from
Tower top discharge, obtains the first tower top rectifying liquid after condensation.
Wherein, the tower top pressure of first rectifying column 21 can be 50~120KPa, such as 70KPa, 90KPa, 110KPa etc.；
The tower top temperature of first rectifying column 21 can be 90~130 DEG C, such as 100 DEG C, 110 DEG C, 120 DEG C etc.；First rectifying column 21
Plate theory series can be 60~120, such as 70,90,100,110 etc..
First tower top rectifying liquid enters Second distillation column 22 and carries out the second rectification process, and low-boiling-point substance therein is arranged from tower top
Out, tower reactor collects high-purity chloro for disilane.
The tower top pressure of Second distillation column 22 can be 40~100KPa, such as 50KPa, 70KPa, 90KPa etc.；Second essence
The tower top temperature for evaporating tower 22 can be for 90~110 DEG C, such as 95 DEG C, 100 DEG C, 105 DEG C etc.；The plate theory of Second distillation column 22
Series can be 70~90, such as 75,80,85 etc..
High-purity chloro enters reactor 30 for disilane and is reacted, and is discharged at the top of reacting rear material autoreactor 30, into
Enter third distillation column 23 and carries out third rectification process, it is reaction residual solvent therein, high boiling point by-products produced from tower reactor discharge, tower top
Extraction includes the material of disilane.Third distillation column 23 is weight-removing column, and the tower top temperature of third distillation column 23 is -10~10 DEG C.
In an embodiment, reactor 30 can be micro passage reaction, and reactor material is metal, glass, carbonization
The materials such as silicon, inside reactor channel diameter are 0.5~10 micron, by reducing reaction channel, improve the mass tranfer coefficient of reaction.
Material comprising disilane enters the 4th rectifying column 24, and the tower top temperature of the 4th rectifying column 24 of control is -50~-30
DEG C, low-boiling products of the boiling point lower than -50~-30 DEG C are discharged from tower top, and tower reactor produces material and enters the 5th rectifying column 25.Control
5th rectifying column, 25 tower top temperature is -20~-15 DEG C, and low-boiling products of the boiling point lower than -20~-15 DEG C are discharged from tower top, tower
Kettle output 4N disilane.
Wherein, impurity collector 40 respectively with the tower reactor of first rectifying column 21, the tower top of Second distillation column 22, third rectifying
The tower top of the tower reactor of tower 23, the tower top of the 4th rectifying column 24 and the 5th rectifying column 25 is connected, so that the impurity of each rectifying column discharge
Impurity collector 40 is eventually entered into be collected.
For the purity for further increasing disilane product, the disilane that the 5th rectifying column 25 is discharged can be sequentially sent into filling
The absorber 31 of active charcoal and the absorber 32 for being filled with molecular sieve carry out adsorption and purification processing, obtain 5N disilane.
Unless limited otherwise, term used herein is the normally understood meaning of those skilled in the art.
Embodiment described in the invention is merely for exemplary purpose, the protection scope being not intended to limit the invention,
Those skilled in the art can be made within the scope of the invention various other replacements, changes and improvements, thus, the present invention is not limited to
Above embodiment, and be only defined by the claims.
Claims (10)
1. a kind of preparation method of disilane, includes the following steps：
The chloro disilane by-product that improved Siemens generate is provided；
The by-product is filtered, filtrate is obtained；
By the filtrate by rectification process, the refined solution of chloro disilane is obtained；And
The chloro disilane in the refined solution is restored, the disilane is made.
2. according to the method described in claim 1, wherein, the rectification process includes at the first rectification process and the second rectifying
Reason.
3. according to the method described in claim 2, wherein, first rectification process carries out in first rectifying column, described
Two rectification process carry out in Second distillation column.
4. according to the method described in claim 3, wherein, the tower top pressure of the first rectifying column is 50~120KPa, tower top
Temperature is 90~130 DEG C, and plate theory series is 60~120.
5. according to the method described in claim 3, wherein, the tower top pressure of the Second distillation column is 40~100KPa, tower top
Temperature is 90~110 DEG C, and plate theory series is 70~90.
6. according to the method described in claim 1, wherein, by lithium aluminium hydride reduction, sodium aluminum hydride or diethylaluminum hydride with it is described
Disilane is made in the reduction reaction of chloro disilane.
7. according to the method described in claim 6, wherein, further include will react resulting disilane by third rectification process,
4th rectification process and the 5th rectification process are purified.
8. according to the method described in claim 7, wherein, the third rectification process carries out in third distillation column, described
Four rectification process carry out in the 4th rectifying column, and the 5th rectification process carries out in the 5th rectifying column, the third rectifying
Tower is connected by tower top with the 4th rectifying column, and the 4th rectifying column is connected by tower bottom with the 5th rectifying column
It is logical.
9. the tower top temperature of the third distillation column is -10~10 DEG C according to the method described in claim 8, wherein, described the
The tower top temperature of four rectifying columns is -50~-30 DEG C, and the tower top temperature of the 5th rectifying column is -20~-15 DEG C.
10. method according to any one of claims 6 to 9, wherein including passing through molecular sieve and/or active carbon to anti-
Resulting disilane is answered to carry out adsorption treatment.
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| CN201810903987.6A CN108862282A (en) | 2018-08-09 | 2018-08-09 | The preparation method of disilane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109399644A (en) * | 2018-12-25 | 2019-03-01 | 洛阳中硅高科技有限公司 | The preparation method of disilane |
| CN109437208A (en) * | 2018-12-25 | 2019-03-08 | 洛阳中硅高科技有限公司 | The preparation facilities of disilane |
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| CN106946261A (en) * | 2017-04-06 | 2017-07-14 | 洛阳中硅高科技有限公司 | The retracting device of disilicone hexachloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106946261A (en) * | 2017-04-06 | 2017-07-14 | 洛阳中硅高科技有限公司 | The retracting device of disilicone hexachloride |
| CN106966397A (en) * | 2017-04-06 | 2017-07-21 | 洛阳中硅高科技有限公司 | The recovery method of disilicone hexachloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109399644A (en) * | 2018-12-25 | 2019-03-01 | 洛阳中硅高科技有限公司 | The preparation method of disilane |
| CN109437208A (en) * | 2018-12-25 | 2019-03-08 | 洛阳中硅高科技有限公司 | The preparation facilities of disilane |
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Application publication date: 20181123 |