CN117735557A - Method for purifying diiodosilane - Google Patents
Method for purifying diiodosilane Download PDFInfo
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- CN117735557A CN117735557A CN202311750938.0A CN202311750938A CN117735557A CN 117735557 A CN117735557 A CN 117735557A CN 202311750938 A CN202311750938 A CN 202311750938A CN 117735557 A CN117735557 A CN 117735557A
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- diiodosilane
- rectification
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- purifying
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- AIHCVGFMFDEUMO-UHFFFAOYSA-N diiodosilane Chemical compound I[SiH2]I AIHCVGFMFDEUMO-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000012535 impurity Substances 0.000 claims abstract description 49
- 238000009835 boiling Methods 0.000 claims abstract description 17
- 238000007711 solidification Methods 0.000 claims abstract description 16
- 230000008023 solidification Effects 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000012159 carrier gas Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 90
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims description 42
- 239000012528 membrane Substances 0.000 claims description 35
- 239000002121 nanofiber Substances 0.000 claims description 35
- 239000004642 Polyimide Substances 0.000 claims description 30
- 229920001721 polyimide Polymers 0.000 claims description 30
- 239000002131 composite material Substances 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 12
- 229920005575 poly(amic acid) Polymers 0.000 claims description 9
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 238000010041 electrostatic spinning Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 9
- 239000002243 precursor Substances 0.000 abstract description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910000077 silane Inorganic materials 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 8
- 229910052627 muscovite Inorganic materials 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 238000011049 filling Methods 0.000 description 7
- 229910052604 silicate mineral Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 150000003961 organosilicon compounds Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- IDIOJRGTRFRIJL-UHFFFAOYSA-N iodosilane Chemical compound I[SiH3] IDIOJRGTRFRIJL-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012686 silicon precursor Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BBTGUNMUUYNPLH-UHFFFAOYSA-N 5-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 BBTGUNMUUYNPLH-UHFFFAOYSA-N 0.000 description 1
- 229910052849 andalusite Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention relates to the field of purification of electronic precursors, in particular to a method for purifying diiodosilane, which comprises the following steps: (S.1) removing air remained in the rectification purifier; (S.2) placing the crude diiodosilane in a rectification purifier, gradually reducing the temperature of the rectification purifier to the solidification critical temperature of the diiodosilane, and continuously introducing carrier gas into the crude diiodosilane under the stirring condition; (S.3) further reducing the temperature of the rectification purifier to solidify diiodosilane, and simultaneously decompressing the interior of the rectification purifier to remove low-boiling impurities; (S.4) rectifying the diiodosilane, and collecting fractions to obtain the electronic grade diiodosilane. According to the method, the temperature in the rectification purifier is accurately reduced to the solidification critical temperature of diiodosilane and the temperature below the solidification point in the rectification process, so that the content of low-boiling-point impurities in the crude diiodosilane can be effectively reduced, and the electronic grade diiodosilane is finally prepared.
Description
Technical Field
The invention relates to the field of purification of electronic precursors, in particular to a method for purifying diiodosilane.
Background
Diiodosilane is an organosilicon compound with the chemical formula SiI 2 H 2 . The organic silicon reagent is a pink, pale yellow and light red inflammable liquid under the conditions of normal temperature and normal pressure, has a pungent smell, and can be used as an important intermediate in organic synthesis and semiconductor materials.
In the field of organic synthesis, diiodosilane is an important organosilicon reagent that can be used to synthesize various organosilicon compounds containing Si-I bonds (e.g., organosilicon compounds such as silanes, silanol, silyl ether, etc.). The organosilicon compounds have important application in the fields of medicine synthesis, material science and the like.
In the semiconductor field, because diiodosilane can generate more active silicon free radicals under the plasma enhancement compared with other silicon precursors, the free radicals have the characteristics of low reaction chamber temperature and controllable pressure operation on the premise of keeping high deposition rate. Therefore, diiodosilane can greatly reduce vapor deposition temperature and provide superior electrical properties, stability and durability to the resulting silicon film, as compared to other silicon precursors. Diiodosilanes are thus listed as critical silicon source materials spanning from 10 nm linewidth to 6 nm linewidth processes.
The purity of diiodosilane is critical to the semiconductor field. The diiodosilane with high purity can ensure the surface modification effect and chemical stability of the semiconductor material, reduce the introduction of impurities in the preparation process of the semiconductor device, and is beneficial to improving the performance and reliability of the semiconductor device. Therefore, high purity diiodosilane is critical for semiconductor material preparation.
At present, due to the limitation of the preparation method, impurities such as monoiodo silane, hydrogen iodide, benzene and the like are often generated in the process of preparing diiodo silane. In order to remove these impurities, a distillation method is generally used. However, these methods have certain limitations in terms of purification efficiency, cost, and environmental friendliness. For example, the number of theoretical plates in the existing distillation process is large, and about 30-50 theoretical plates are required. Therefore, the prior art has certain problems and limitations in the process of purifying diiodosilane, and further seeks to provide a more efficient, low-cost and environment-friendly purification method.
Disclosure of Invention
The invention provides a method for purifying diiodosilane to overcome the defects of low efficiency and high cost in the purification process of diiodosilane in the prior art.
In order to achieve the aim of the invention, the invention is realized by the following technical scheme:
a method for purifying diiodosilane comprising the steps of:
(S.1) carrying out a circulation step of vacuumizing and introducing carried gas in the rectification purifier so as to remove the air remained in the rectification purifier;
(S.2) placing the crude diiodosilane in a rectification purifier, gradually reducing the temperature of the rectification purifier to the solidification critical temperature of the diiodosilane, and continuously introducing carrier gas into the crude diiodosilane under the stirring condition;
(S.3) further reducing the temperature of the rectification purifier to solidify diiodosilane, and simultaneously decompressing the interior of the rectification purifier to remove low-boiling impurities;
and (S.4) simultaneously raising the internal temperature and pressure of the rectification purifier, rectifying the diiodosilane, and collecting fractions to obtain the electronic grade diiodosilane.
The inventors of the present application have found by chance during the purification of diiodosilane using a rectification method: some impurities (such as monoiodo silane and benzene) in diiodo silane can form an azeotrope with diiodo silane in the rectification process, so that a part of impurities cannot be separated from diiodo silane all the time, and the quality of diiodo silane cannot be further improved.
Aiming at the technical problem, the rectification method is improved in a targeted manner. Firstly, the temperature of the rectification purifier is reduced to the solidification critical temperature of diiodosilane in a targeted manner, and under the temperature condition, diiodosilane is at the critical point of solid and liquid, at the moment, part of diiodosilane in the rectification purifier is solid, and the other part of diiodosilane is liquid (namely, similar to water forms an ice-water mixture at 0 ℃). Under these conditions, the saturated vapor pressure of diiodosilane decreases significantly, but the saturated vapor pressure of impurities doped in diiodosilane does not decrease significantly, and therefore, the total saturated vapor pressure in the rectification purifier decreases to some extent, but the ratio of the saturated vapor pressure partial pressure of impurities increases significantly.
In addition, the diiodosilane is not completely condensed into solid under the condition of the solidification critical temperature of the diiodosilane, so that impurity gas is not coated by the diiodosilane solid, and the problem that impurities cannot be removed due to the coating of the diiodosilane solid is avoided.
Under the condition, the continuous introduction of the carrier gas into the crude diiodosilane can enable impurities in the diiodosilane to be continuously carried out from the diiodosilane along with the carrier gas, so that the content of the impurities in the crude diiodosilane can be greatly reduced.
Subsequently, in order to further reduce the impurity content in diiodosilane, the temperature of the rectification purifier is further reduced so that diiodosilane located inside the rectification purifier is solidified. Under these conditions, the partial pressure of the vapor pressure of diiodosilane is further reduced, so that the total saturated vapor pressure inside the rectification purifier is mainly formed by impurities doped inside diiodosilane. At the same time, as the pressure inside the rectification purifier decreases, the low boiling impurities in diiodosilane can thus be further removed.
After the twice cooling and impurity removal, most of impurities in the diiodosilane are removed, and only some impurities with high boiling point remain in the diiodosilane. Therefore, in order to remove the high-boiling-point impurities, the pressure in the rectification purifier is increased, so that the difference of boiling points between diiodosilane and the high-boiling-point impurities is increased, the difficulty in separating diiodosilane and the high-boiling-point impurities through rectification treatment is reduced, and electronic-grade diiodosilane can be finally obtained.
Preferably, in the step (S.2), the critical temperature for solidification is-1 ℃ to 0 ℃.
In the temperature range, diiodosilane starts to solidify, and the volatility of diiodosilane is relatively reduced, so that the loss of diiodosilane is reduced and the purity of diiodosilane is improved in the subsequent step of removing low-boiling-point substances. And nitrogen is introduced in the solidification critical temperature range, so that the nitrogen can be ensured to be fully contacted with diiodosilane, and impurities in the solidification process can be removed.
Preferably, the flow rate of the carrier gas in the step (s.2) is 1000 sccm~3000 sccm; the charging time of the carrying gas is 1-5h.
Through continuously introducing nitrogen, the mixing and diffusion of crude diiodosilane and nitrogen can be promoted, the removal of impurities in the solidification process is facilitated, and the purity is improved. By controlling the flow and time of the carried gas, the solidification speed of diiodosilane can be effectively controlled, the problem of product quality caused by too high or too low speed is avoided, and the uniformity and stability of the impurity removal process in the solidification process are ensured.
Preferably, the temperature of the rectification purifier in the step (S.3) is-10 ℃ to-5 ℃.
In this temperature range, diiodosilane remains in a solid state, which facilitates removal of volatile impurities during distillation, while maintaining the diiodosilane in a solidified state.
Preferably, the flow rate of the carrier gas in the step (s.3) is 4000 sccm~6000 sccm; the charging time of the carrying gas is 1-5h.
Preferably, the vacuum degree in the step (S.3) is 50-100Pa.
Preferably, in the step (S.4), the internal pressure of the rectification purifier is equal to the external atmospheric pressure, and the fraction collection temperature is 149-150 ℃.
Preferably, the carrier gas is any one of nitrogen, helium and argon.
Preferably, the rectification purifier is also filled with a polyimide/silicate composite nanofiber membrane.
Preferably, the preparation method of the polyimide/silicate composite nanofiber membrane comprises the following steps:
(1) Mixing dianhydride monomer, diamine monomer and silicate with a solvent, and reacting to obtain a polyamic acid/silicate mixed solution;
(2) Carrying out electrostatic spinning on the polyamic acid/silicate mixed solution to obtain a polyamic acid/silicate nanofiber membrane;
(3) And performing thermal imidization reaction on the polyamide acid/silicate nanofiber membrane to obtain the polyimide/silicate composite nanofiber membrane.
Preferably, the silicate is a layered silicate.
Preferably, the layered silicate is one or a combination of a plurality of mica, talcum and montmorillonite.
Therefore, the invention has the following beneficial effects:
according to the method, the temperature in the rectification purifier is accurately reduced to the solidification critical temperature of diiodosilane and the temperature below the solidification point in the rectification process, so that the content of low-boiling-point impurities in the crude diiodosilane can be effectively reduced, then high-boiling-point impurities doped in diiodosilane are further removed in a single-tower rectification mode, and finally the electronic grade diiodosilane is prepared.
Drawings
FIG. 1 is an electron microscope image of a polyimide/silicate composite nanofiber membrane prepared in an embodiment of the present invention.
FIG. 2 is a chart of a gas phase detection of crude diiodosilane (99.5% purity) without purification in the examples of the present invention.
FIG. 3 is a graph of the gas detection of purified electronic grade diiodosilane according to the present invention.
Detailed Description
The invention is further described below in connection with specific embodiments. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
[ preparation of polyimide/silicate composite nanofiber Membrane ]
Preparation example 1
Preparation of polyimide/silicate composite nanofiber membrane (a): the preparation method comprises the following steps:
(1) 4.0046g (0.02 mo 1) of 4,4 '-diphenylether diamine (ODA), 8.0462g (0.02 moI) of 4,4' -terephthaloyl bisphthalic anhydride (HQDA) and 3g of muscovite powder are added into a three-necked flask, 60ml of LDMAc is added, and the mixture is strongly stirred, reacted for 6 hours at-5 ℃ and then heated to 10 ℃ for 6 hours, thus obtaining a polyamic acid/muscovite mixed solution.
(2) And carrying out electrostatic spinning (the voltage is 20kV, and the distance between a spray needle point and a roller receiver is 20 cm) on the prepared polyamic acid/muscovite mixed solution to obtain the polyamic acid/silicate nanofiber membrane.
(3) Removing the solvent in a vacuum oven at 60 ℃ for 4 hours, performing thermal imidization according to imidization procedures of 120 ℃/1 hour, 200 ℃/1 hour, 250 ℃/1 hour and heating rate of 1 ℃/min, annealing, cooling to room temperature, and taking out to obtain the polyimide/silicate composite nanofiber membrane (A). An electron microscope photograph of the prepared polyimide/silicate composite nanofiber membrane (A) is shown in figure 1.
Preparation example 2
Preparation 2 differs from preparation 1 in that: and (3) replacing the muscovite powder in the step (1) with montmorillonite powder to obtain the polyimide/silicate composite nanofiber membrane (B).
Preparation example 3
Preparation 3 differs from preparation 1 in that: and (3) replacing the muscovite powder in the step (1) with talcum powder to obtain the polyimide/silicate composite nanofiber membrane (C).
Preparation example 4
Preparation example 4 differs from preparation example 1 in that: the addition of the muscovite powder in the step (1) is canceled, and the polyimide nanofiber membrane (D) is obtained.
Preparation example 5
Preparation 5 differs from preparation 1 in that: and (3) replacing the muscovite powder in the step (1) with the andalusite powder (cyclic structure silicate mineral) to obtain the polyimide/silicate composite nanofiber membrane (E).
Preparation example 6
Preparation example 6 differs from preparation example 1 in that: and (3) replacing the muscovite powder in the step (1) with feldspar powder (rack-like structure silicate mineral) to obtain the polyimide/silicate composite nanofiber membrane (F).
Example 1
A method for purifying diiodosilane comprising the steps of:
(S.1) vacuumizing the rectification purifier to a bottom pressure (about 10 pa), then introducing nitrogen into the rectification purifier until the internal pressure of the rectification purifier is equal to the external pressure, and circulating for 5 times, thereby removing the residual air in the rectification purifier;
(S.2) placing crude diiodosilane (commercially available, purity is 99.5%) silane into a rectification purifier, gradually reducing the temperature of the rectification purifier to-1-0 ℃, and continuously introducing nitrogen with the flow rate of 2000 sccm into the crude diiodosilane at the stirring speed of 100 rmp for 3 hours;
(S.3) further reducing the temperature of the rectification purifier to-8 ℃ to solidify diiodosilane, vacuumizing the interior of the rectification purifier to 80-Pa, and simultaneously adjusting the nitrogen inlet flow to 5000 sccm and the nitrogen inlet time to 3 hours so as to remove low-boiling impurities;
and (S.4) simultaneously lifting the internal pressure of the rectification purifier to be equal to the external atmospheric pressure, simultaneously lifting the internal temperature of the rectification purifier to enable diiodosilane to flow back, controlling the number of tower plates of the rectification purifier to be 20, rectifying, removing low-boiling-point fractions, and collecting fractions with the temperature of 149-150 ℃ to obtain electronic-grade diiodosilane.
FIG. 2 is a chart showing the gas phase detection of crude diiodosilane (purity: 99.5%) without purification in the examples of the present invention, wherein the crude diiodosilane without purification (purity: 99.5%) contains a large number of impurity peaks. The gas-phase detection spectrum of the electronic-grade diiodosilane purified in example 1 of the present invention is shown in fig. 2, and it is understood from the figure that the originally existing impurity peaks have been substantially removed, and only the diiodosilane peaks remain. The diiodosilane purity was 99.99% calculated according to the gas chromatography area normalization method.
Example 2
A method for purifying diiodosilane comprising the steps of:
(S.1) vacuumizing the rectification purifier to a bottom pressure (about 10 pa), then introducing nitrogen into the rectification purifier until the internal pressure of the rectification purifier is equal to the external pressure, and circulating for 5 times, thereby removing the residual air in the rectification purifier;
(S.2) placing crude diiodosilane (commercially available, purity is 99.5%) silane into a rectification purifier, gradually reducing the temperature of the rectification purifier to-1-0 ℃, and continuously introducing nitrogen with the flow of 1000 sccm into the crude diiodosilane at the stirring speed of 100 rmp for 5 hours;
(S.3) further reducing the temperature of the rectification purifier to-5 ℃ to solidify diiodosilane, vacuumizing the interior of the rectification purifier to a vacuum degree of 100Pa, and simultaneously adjusting the nitrogen gas inlet flow to 4000 sccm and the nitrogen gas inlet time to 5 hours so as to remove low-boiling-point impurities;
and (S.4) simultaneously lifting the internal pressure of the rectification purifier to be equal to the external atmospheric pressure, simultaneously lifting the internal temperature of the rectification purifier to enable diiodosilane to flow back, controlling the number of tower plates of the rectification purifier to be 20, rectifying, removing low-boiling-point fractions, and collecting fractions with the temperature of 149-150 ℃ to obtain electronic-grade diiodosilane.
Example 3
A method for purifying diiodosilane comprising the steps of:
(S.1) vacuumizing the rectification purifier to a bottom pressure (about 10 pa), then introducing nitrogen into the rectification purifier until the internal pressure of the rectification purifier is equal to the external pressure, and circulating for 5 times, thereby removing the residual air in the rectification purifier;
(S.2) placing crude diiodosilane (commercially available, purity is 99.5%) silane into a rectification purifier, gradually reducing the temperature of the rectification purifier to-1-0 ℃, and continuously introducing nitrogen with the flow rate of 3000 sccm into the crude diiodosilane at the stirring speed of 100 rmp for 1h;
(S.3) further reducing the temperature of the rectification purifier to minus 10 ℃ to solidify diiodosilane, vacuumizing the interior of the rectification purifier to the vacuum degree of 50Pa, and simultaneously adjusting the nitrogen gas inlet flow to 6000 sccm and the nitrogen gas inlet time to 3 hours so as to remove low-boiling-point impurities;
and (S.4) simultaneously lifting the internal pressure of the rectification purifier to be equal to the external atmospheric pressure, simultaneously lifting the internal temperature of the rectification purifier to enable diiodosilane to flow back, controlling the number of tower plates of the rectification purifier to be 20, rectifying, removing low-boiling-point fractions, and collecting fractions with the temperature of 149-150 ℃ to obtain electronic-grade diiodosilane.
Example 4
A method for purifying diiodosilane comprising the steps of:
filling the polyimide/silicate composite nanofiber membrane (A) into a rectification purifier, vacuumizing the rectification purifier to a bottom pressure (about 10 pa), then introducing nitrogen into the rectification purifier until the pressure in the rectification purifier is equal to the external pressure, and circulating for 5 times, thereby removing the air remained in the rectification purifier;
(S.2) placing crude diiodosilane (commercially available, purity is 99.5%) silane into a rectification purifier, gradually reducing the temperature of the rectification purifier to-1-0 ℃, and continuously introducing nitrogen with the flow rate of 2000 sccm into the crude diiodosilane at the stirring speed of 100 rmp for 3 hours;
(S.3) further reducing the temperature of the rectification purifier to-8 ℃ to solidify diiodosilane, vacuumizing the interior of the rectification purifier to 80-Pa, and simultaneously adjusting the nitrogen inlet flow to 5000 sccm and the nitrogen inlet time to 3 hours so as to remove low-boiling impurities;
and (S.4) simultaneously lifting the internal pressure of the rectification purifier to be equal to the external atmospheric pressure, simultaneously lifting the internal temperature of the rectification purifier to enable diiodosilane to flow back and contact with the polyimide/silicate composite nanofiber membrane (A), controlling the number of tower plates of the rectification purifier to be 15 for rectification treatment, and collecting fractions with the temperature of 149-150 ℃ after removing low-boiling fractions to obtain the electronic grade diiodosilane.
Example 5
A method for purifying diiodosilane comprising the steps of:
filling the polyimide/silicate composite nanofiber membrane (B) into a rectification purifier, vacuumizing the rectification purifier to a bottom pressure (about 10 pa), then introducing nitrogen into the rectification purifier until the pressure in the rectification purifier is equal to the external pressure, and circulating for 5 times, thereby removing the air remained in the rectification purifier;
(S.2) placing crude diiodosilane (commercially available, purity is 99.5%) silane into a rectification purifier, gradually reducing the temperature of the rectification purifier to-1-0 ℃, and continuously introducing nitrogen with the flow rate of 2000 sccm into the crude diiodosilane at the stirring speed of 100 rmp for 3 hours;
(S.3) further reducing the temperature of the rectification purifier to-8 ℃ to solidify diiodosilane, vacuumizing the interior of the rectification purifier to 80-Pa, and simultaneously adjusting the nitrogen inlet flow to 5000 sccm and the nitrogen inlet time to 3 hours so as to remove low-boiling impurities;
and (S.4) simultaneously lifting the internal pressure of the rectification purifier to be equal to the external atmospheric pressure, simultaneously lifting the internal temperature of the rectification purifier to enable diiodosilane to flow back and contact with the polyimide/silicate composite nanofiber membrane (B), controlling the number of tower plates of the rectification purifier to be 15 for rectification treatment, and collecting fractions with the temperature of 149-150 ℃ after removing low-boiling fractions to obtain the electronic grade diiodosilane.
Example 6
A method for purifying diiodosilane comprising the steps of:
filling the polyimide/silicate composite nanofiber membrane (C) into a rectification purifier, vacuumizing the rectification purifier to a bottom pressure (about 10 pa), then introducing nitrogen into the rectification purifier until the pressure in the rectification purifier is equal to the external pressure, and circulating for 5 times, thereby removing the air remained in the rectification purifier;
(S.2) placing crude diiodosilane (commercially available, purity is 99.5%) silane into a rectification purifier, gradually reducing the temperature of the rectification purifier to-1-0 ℃, and continuously introducing nitrogen with the flow rate of 2000 sccm into the crude diiodosilane at the stirring speed of 100 rmp for 3 hours;
(S.3) further reducing the temperature of the rectification purifier to-8 ℃ to solidify diiodosilane, vacuumizing the interior of the rectification purifier to 80-Pa, and simultaneously adjusting the nitrogen inlet flow to 5000 sccm and the nitrogen inlet time to 3 hours so as to remove low-boiling impurities;
and (S.4) simultaneously lifting the internal pressure of the rectification purifier to be equal to the external atmospheric pressure, simultaneously lifting the internal temperature of the rectification purifier to enable diiodosilane to flow back and contact with the polyimide/silicate composite nanofiber membrane (C), controlling the number of tower plates of the rectification purifier to be 15, rectifying, removing low-boiling-point fractions, and collecting the fractions with the temperature of 149-150 ℃ to obtain the electronic-grade diiodosilane.
Comparative example 1
Filling the polyimide/silicate composite nanofiber membrane (A) into a rectification purifier, vacuumizing the rectification purifier to a bottom pressure (about 10 pa), then introducing nitrogen into the rectification purifier until the pressure in the rectification purifier is equal to the external pressure, and circulating for 5 times, thereby removing the air remained in the rectification purifier;
and (S.2) placing crude diiodosilane (commercially available, 99.5% pure) in a rectification purifier, simultaneously lifting the internal temperature of the rectification purifier to reflux the diiodosilane, controlling the number of tower plates of the rectification purifier to be 30 for rectification treatment, removing low-boiling-point fractions, and collecting the fractions with the temperature of 149-150 ℃ to obtain the electronic grade diiodosilane.
Comparative example 2
A method for purifying diiodosilane comprising the steps of:
(S.1) vacuumizing the rectification purifier to a bottom pressure (about 10 pa), then introducing nitrogen into the rectification purifier until the internal pressure of the rectification purifier is equal to the external pressure, and circulating for 5 times, thereby removing the residual air in the rectification purifier;
(S.2) placing crude diiodosilane (commercially available, purity is 99.5%) silane into a rectification purifier, gradually reducing the temperature of the rectification purifier to-10 ℃, and continuously introducing nitrogen with the flow rate of 2000 sccm into the crude diiodosilane at the stirring speed of 100 rmp for 3 hours;
and (S.3) simultaneously lifting the internal pressure of the rectification purifier to be equal to the external atmospheric pressure, simultaneously lifting the internal temperature of the rectification purifier to reflux diiodosilane, controlling the number of tower plates of the rectification purifier to be 20, rectifying, removing low-boiling-point fractions, and collecting fractions with the temperature of 149-150 ℃ to obtain the electronic grade diiodosilane.
Comparative example 3
A method for purifying diiodosilane comprising the steps of:
filling a polyimide nanofiber membrane (D) into a rectification purifier, vacuumizing the rectification purifier to a bottom pressure (about 10 pa), then introducing nitrogen into the rectification purifier until the internal pressure of the rectification purifier is equal to the external pressure, and circulating for 5 times, so that the air remained in the rectification purifier is removed;
(S.2) placing crude diiodosilane (commercially available, purity is 99.5%) silane into a rectification purifier, gradually reducing the temperature of the rectification purifier to-1-0 ℃, and continuously introducing nitrogen with the flow rate of 2000 sccm into the crude diiodosilane at the stirring speed of 100 rmp for 3 hours;
(S.3) further reducing the temperature of the rectification purifier to-8 ℃ to solidify diiodosilane, vacuumizing the interior of the rectification purifier to 80-Pa, and simultaneously adjusting the nitrogen inlet flow to 5000 sccm and the nitrogen inlet time to 3 hours so as to remove low-boiling impurities;
and (S.4) simultaneously lifting the internal pressure of the rectification purifier to be equal to the external atmospheric pressure, simultaneously lifting the internal temperature of the rectification purifier to enable diiodosilane to flow back and contact with the polyimide nanofiber membrane (D), controlling the number of tower plates of the rectification purifier to be 15 for rectification treatment, and collecting fractions with the temperature of 149-150 ℃ after removing low boiling point fractions to obtain the electronic grade diiodosilane.
Comparative example 4
A method for purifying diiodosilane comprising the steps of:
filling a polyimide/silicate composite nanofiber membrane (E) into a rectification purifier, vacuumizing the rectification purifier to a bottom pressure (about 10 pa), then introducing nitrogen into the rectification purifier until the pressure in the rectification purifier is equal to the external pressure, and circulating for 5 times, thereby removing residual air in the rectification purifier;
(S.2) placing crude diiodosilane (commercially available, purity is 99.5%) silane into a rectification purifier, gradually reducing the temperature of the rectification purifier to-1-0 ℃, and continuously introducing nitrogen with the flow rate of 2000 sccm into the crude diiodosilane at the stirring speed of 100 rmp for 3 hours;
(S.3) further reducing the temperature of the rectification purifier to-8 ℃ to solidify diiodosilane, vacuumizing the interior of the rectification purifier to 80-Pa, and simultaneously adjusting the nitrogen inlet flow to 5000 sccm and the nitrogen inlet time to 3 hours so as to remove low-boiling impurities;
and (S.4) simultaneously lifting the internal pressure of the rectification purifier to be equal to the external atmospheric pressure, simultaneously lifting the internal temperature of the rectification purifier to enable diiodosilane to flow back and contact with the polyimide/silicate composite nanofiber membrane (E), controlling the number of tower plates of the rectification purifier to be 15, rectifying, removing low-boiling-point fractions, and collecting the fractions with the temperature of 149-150 ℃ to obtain the electronic-grade diiodosilane.
Comparative example 5
A method for purifying diiodosilane comprising the steps of:
filling a polyimide/silicate composite nanofiber membrane (F) into a rectification purifier, vacuumizing the rectification purifier to a bottom pressure (about 10 pa), then introducing nitrogen into the rectification purifier until the pressure in the rectification purifier is equal to the external pressure, and circulating for 5 times, thereby removing residual air in the rectification purifier;
(S.2) placing crude diiodosilane (commercially available, purity is 99.5%) silane into a rectification purifier, gradually reducing the temperature of the rectification purifier to-1-0 ℃, and continuously introducing nitrogen with the flow rate of 2000 sccm into the crude diiodosilane at the stirring speed of 100 rmp for 3 hours;
(S.3) further reducing the temperature of the rectification purifier to-8 ℃ to solidify diiodosilane, vacuumizing the interior of the rectification purifier to 80-Pa, and simultaneously adjusting the nitrogen inlet flow to 5000 sccm and the nitrogen inlet time to 3 hours so as to remove low-boiling impurities;
and (S.4) simultaneously lifting the internal pressure of the rectification purifier to be equal to the external atmospheric pressure, simultaneously lifting the internal temperature of the rectification purifier to enable diiodosilane to flow back and contact with the polyimide/silicate composite nanofiber membrane (F), controlling the number of tower plates of the rectification purifier to be 15 for rectification treatment, and collecting fractions with the temperature of 149-150 ℃ after removing low-boiling fractions to obtain the electronic grade diiodosilane.
Purity tests were conducted on diiodosilanes prepared in examples 1 to 6 and comparative examples 1 to 5, and the test results are shown in table 1 below:
TABLE 1
。
From the above test results, it was found that the content of impurities (monoiodo silane, hydrogen iodide, and benzene) in diiodo silane can be greatly reduced by the method in the present application, indicating that diiodo silane can be effectively purified by the method in the present application.
As is clear from comparative example 1, it is difficult to reduce the impurity in diiodosilane to a desired concentration using the conventional rectification means in comparative example 1, since the impurity can form an azeotrope with diiodosilane.
In comparative example 2, although there was a step of freezing diiodosilane and then purging with nitrogen, since a part of impurities after direct freezing diiodosilane was covered with diiodosilane, a part of impurities was co-doped with diiodosilane, and therefore the reduction of the part of impurities was limited, and the removal of impurities was not possible due to the formation of an azeotrope even when rectification was performed at a later stage in time.
The difference between comparative examples 3 to 5 and examples is that the types of silicate in the polyimide/silicate composite nanofiber membrane are replaced, and after the original layered silicate is replaced by the silicate mineral with a ring structure and the silicate mineral with a rack structure, the original layered silicate (mica, talc and montmorillonite) has better adsorption effect on impurities in diiodosilane than the silicate mineral with a ring structure and the silicate mineral with a rack structure, so that diiodosilane can be favorably provided with higher purity, and the application of diiodosilane in the fields of electrons and semiconductors is facilitated.
The examples are intended to be illustrative only of the invention and any modifications, additions or equivalent substitutions made by those skilled in the art based on the embodiments are within the scope of the invention as claimed.
Claims (10)
1. The method for purifying diiodosilane is characterized by comprising the following steps:
(S.1) carrying out vacuumizing in a rectification purifier and introducing a circulation step of carrying gas, so as to remove the air remained in the rectification purifier;
(S.2) placing the crude diiodosilane in a rectification purifier, gradually reducing the temperature of the rectification purifier to the solidification critical temperature of the diiodosilane, and continuously introducing carrier gas into the crude diiodosilane under the stirring condition;
(S.3) further reducing the temperature of the rectification purifier to solidify diiodosilane, and simultaneously decompressing the interior of the rectification purifier to remove low-boiling impurities;
and (S.4) simultaneously raising the internal temperature and pressure of the rectification purifier, rectifying the diiodosilane, and collecting fractions to obtain the electronic grade diiodosilane.
2. A process for purifying diiodosilane according to claim 1, wherein,
the critical temperature for solidification in the step (S.2) is-1-0 ℃.
3. A process for purifying diiodosilane according to claim 1 or 2, characterized in that,
the inlet flow rate of the carried gas in the step (S.2) is 1000 sccm~3000 sccm; the nitrogen gas is introduced for 1-5h.
4. A process for purifying diiodosilane according to claim 1, wherein,
the temperature of the rectifying purifier in the step (S.3) is-10 ℃ to-5 ℃.
5. A process for purifying diiodosilane according to claim 1, wherein,
the inlet flow rate of the carried gas in the step (S.3) is 4000 sccm~6000 sccm; the nitrogen gas is introduced for 3-5h.
6. A process for purifying diiodosilane according to claim 1, 4 or 5, characterized in that,
and (3) the vacuum degree in the step (S.3) is 50-100Pa.
7. A process for purifying diiodosilane according to claim 1, wherein,
in the step (S.4), the internal pressure of the rectification purifier is equal to the external atmospheric pressure, and the fraction collection temperature is 149-150 ℃.
8. A process for purifying diiodosilane according to claim 1, wherein,
the carrying gas is any one of nitrogen, helium and argon.
9. A process for purifying diiodosilane according to claim 1, wherein,
the rectification purifier is also filled with polyimide/silicate composite nanofiber membranes.
10. A method for purifying diiodosilane according to claim 9, wherein,
the preparation method of the polyimide/silicate composite nanofiber membrane comprises the following steps:
(1) Mixing dianhydride monomer, diamine monomer and silicate with a solvent, and reacting to obtain a polyamic acid/silicate mixed solution;
(2) Carrying out electrostatic spinning on the polyamic acid/silicate mixed solution to obtain a polyamic acid/silicate nanofiber membrane;
(3) And performing thermal imidization reaction on the polyamide acid/silicate nanofiber membrane to obtain the polyimide/silicate composite nanofiber membrane.
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