WO2012056621A1 - クロロシラン類の精製方法 - Google Patents
クロロシラン類の精製方法 Download PDFInfo
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- WO2012056621A1 WO2012056621A1 PCT/JP2011/004937 JP2011004937W WO2012056621A1 WO 2012056621 A1 WO2012056621 A1 WO 2012056621A1 JP 2011004937 W JP2011004937 W JP 2011004937W WO 2012056621 A1 WO2012056621 A1 WO 2012056621A1
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- chlorosilanes
- distillate
- chlorosilane
- trichlorosilane
- fraction
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- 0 CCCCC1*2C1C*C2 Chemical compound CCCCC1*2C1C*C2 0.000 description 3
- YRNJEIGNLYDKQJ-UHFFFAOYSA-N CCC1C=CC=CC1 Chemical compound CCC1C=CC=CC1 YRNJEIGNLYDKQJ-UHFFFAOYSA-N 0.000 description 1
- WLJXUWKOEVKMGD-UHFFFAOYSA-N ClC1c2ccccc2CC1 Chemical compound ClC1c2ccccc2CC1 WLJXUWKOEVKMGD-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/10778—Purification
- C01B33/10794—Purification by forming addition compounds or complexes, the reactant being possibly contained in an adsorbent
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
- C01B33/10742—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material
- C01B33/10757—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material with the preferential formation of trichlorosilane
- C01B33/10763—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof prepared by hydrochlorination of silicon or of a silicon-containing material with the preferential formation of trichlorosilane from silicon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/10778—Purification
Definitions
- the present invention relates to a method for purifying chlorosilanes, and more particularly, to a method for efficiently removing donor impurities and acceptor impurities contained in chlorosilanes to obtain high-purity chlorosilanes.
- Semiconductor grade high-purity polycrystalline silicon is usually produced by a CVD method called “Siemens method” using a chlorosilane gas mainly composed of trichlorosilane in the presence of hydrogen as a raw material. Accordingly, chlorosilanes that are raw materials for high-purity polycrystalline silicon are also required to have extremely high purity.
- the impurities contained in the raw material chlorosilanes are impurities such as phosphorus and arsenic that serve as donors in the silicon crystal, or impurities such as boron and aluminum that serve as acceptors, these impurities are present in trace amounts. Even so, it significantly affects the electrical properties (resistivity) of the polycrystalline silicon produced. For this reason, provision of a technique for efficiently removing the donor impurities and acceptor impurities contained in the raw material chlorosilanes to achieve high purity has great practical significance.
- chlorosilanes for producing polycrystalline silicon are chlorosilane distillates obtained from metallurgical grade silicon containing a relatively large amount of impurities (so-called metal grade silicon, hereinafter referred to as “metal silicon”) by a known method. After being obtained, the chlorosilane distillate is further purified by a technique such as distillation to be purified.
- the above-mentioned donor impurities and acceptor impurities are contained in metal silicon in the order of several hundred ppb (atomic) to several hundred ppm (atomic) in terms of atomic ratio. For this reason, these impurities are not sufficiently removed in the purification process of chlorosilane distillates, and donor impurities and acceptor impurities remain in the finally obtained chlorosilanes. The problem of degrading the quality of polycrystalline silicon can arise.
- a hydrogenation step of reacting a tetrachlorosilane (SiCl 4 ) -containing material with hydrogen in the presence of metallic silicon to obtain a chlorosilane distillate containing trichlorosilane (SiHCl 3 ).
- a chlorosilane distillate is a fraction of crude chlorosilanes, which are products synthesized by a hydrogenation reaction, and is generally a dichlorosilane (SiH 2 Cl 2 ), trichlorosilane (SiHCl 3 ), tetrachlorosilane ( It is a mixture mainly composed of chlorosilanes such as SiCl 4 ).
- a chlorination step is performed in which metal silicon and hydrogen chloride are brought into contact with each other in the presence of a catalyst to perform a chlorination reaction to obtain a chlorosilane distillate containing trichlorosilane.
- a catalyst to perform a chlorination reaction to obtain a chlorosilane distillate containing trichlorosilane.
- a chlorosilane distillate is a fraction of crude chlorosilanes, which is a product synthesized by a chlorination reaction.
- chlorosilanes such as dichlorosilane, trichlorosilane, and tetrachlorosilane are generally the main components. It is a mixture.
- Donor impurities and acceptor impurities contained in metallic silicon are considered to be mixed in the crude chlorosilanes as various forms of compounds, etc. by being hydrogenated or chlorinated simultaneously with the production of the crude chlorosilanes. ing.
- Such crude chlorosilanes are purified to obtain high-purity chlorosilanes. If the boiling point of a compound such as a donor impurity or an acceptor impurity is close to that of trichlorosilane, these impurities are removed by general distillation. It is difficult to separate and remove by a method. If polycrystalline silicon is produced using chlorosilanes with insufficient removal of donor impurities and acceptor impurities as raw materials, polycrystalline silicon having desired characteristics cannot be obtained.
- JP-A-2005-67979 discloses a method of distilling and purifying by adding ethers to chlorosilanes.
- US Pat. No. 3,126,248 discloses a method for removing impurities by adding an organic compound composed of dioxane, benzaldehyde, methyl ethyl ketone, dimethylglyoxime, and valerolactone.
- JP-A-2009-62213 Patent Document 6) discloses that chlorosilanes are reacted with oxygen in the presence of benzaldehyde to convert impurities into high-boiling compounds, and the treated chlorosilanes are distilled.
- a method for separating high-boiling impurities and chlorosilanes is disclosed.
- Patent Document 7 discloses a method in which aluminum chloride is added to chlorosilanes to form an AlCl 3 ⁇ PCl 5 complex, followed by distillation purification.
- Patent Document 8 discloses a method in which an inorganic salt aqueous solution such as TiCl 4 is added at a high concentration to hydrolyze impurities to form a high-boiling compound, followed by distillation purification. ing.
- Patent Document 9 a substance having a lone electron pair (for example, a substance such as propionitrile having a nitrogen atom or benzaldehyde having an oxygen atom), activated carbon, A method is disclosed in which impurities are trapped and removed by immobilizing on an adsorbent such as silica gel and flowing a chlorosilane gas.
- German Patent 1,289,834 Patent Document 10 discloses a method for removing impurities by contacting chlorosilanes with activated alumina in a liquid or vapor state.
- Patent Document 11 discloses a method for removing impurities by bringing chlorosilanes into contact with a metal oxide such as hydrated silica gel or alumina gel.
- Patent Document 12 discloses a method of removing impurities by contacting chlorosilanes with an alkali or alkaline earth fluoride salt.
- a complex is formed by introducing a small amount of oxygen into chlorosilanes and reacting under high temperature conditions, and a new complex is formed by reacting this complex with donor impurities and acceptor impurities.
- a method of obtaining chlorosilanes having a low impurity concentration by separating them in a distillation step of chlorosilanes has also been proposed (see Japanese Patent Publication No. 58-500895 (Patent Document 13)).
- a method of adding an organic substance or a metal chloride to a chlorosilane distillate to produce an adduct with a donor impurity or an acceptor impurity is obtained by combining an adduct with trichlorosilane as a main component.
- chlorosilanes can be purified with high purity by a subsequent distillation step.
- the organic substance that is effective in removing impurities in the purification method of adding an organic substance to a chlorosilane distillate is an organic substance containing an element having a lone pair of electrons.
- organic substances there are considerable restrictions on the selection of such organic substances.
- the added organic matter should not be decomposed very easily during the purification process, and products near the boiling point of chlorosilanes may be reduced by reaction with substances in the chlorosilane distillate. It is also necessary that it does not occur.
- the organic substance containing an element having a lone pair is a solid, it is necessary to consider whether it dissolves at the handling temperature of the chlorosilane distillate and whether it will precipitate due to operating conditions during handling.
- sufficient consideration is necessary to prevent moisture from being mixed at the time of charging. In other words, it is necessary to carefully select an organic substance effective for removing impurities in consideration of various conditions of the purification process.
- Benzaldehyde (C 6 H 5 CHO) is known as an organic substance containing an element having a lone electron pair effective for removing donor impurities and acceptor impurities (see Patent Document 5, Patent Document 6, Patent Document 9, etc.). .
- Benzaldehyde is easy to handle and easily available at the time of addition, but benzaldehydes form a solid high polymer by the following reaction formula, for example, in the presence of a metal chloride such as iron chloride. Since such highly polymerized products are solidified to generate clogs in pipes and containers, it is necessary to periodically stop the production equipment in order to remove the solids.
- the purification method of adding a metal chloride to a chlorosilane distillate is not easy to handle, and has problems such as complicated waste disposal.
- the method of removing impurities contained in chlorosilanes by adsorbing them on alumina, silica gel, activated carbon, etc. requires an apparatus such as an adsorption tower, which complicates the equipment, and makes it easy to support the adsorbate. There is also a problem that there are no problems, such as handling of adsorbate after breakthrough and waste disposal.
- the present invention has been made in view of the problems of the conventional purification method of chlorosilanes as described above, and the object is to remove donor impurities and acceptor impurities from the chlorosilane distillate. It is to provide a technique for reducing the amount.
- the method for purifying chlorosilanes according to the present invention is characterized by comprising the following steps (A) to (C).
- B) The chlorosilane distillate obtained in the hydrogenation step or chlorination step of (A) is treated in the presence of an aldehyde compound represented by the general formula Ar—R—CHO to obtain the chlorosilane distillate Impurity conversion step for converting donor impurities and acceptor impurities contained in the product into high-boiling products (wherein, in the above general formula, Ar is a substituted or unsubstituted aryl group,
- this invention is good also as an aspect provided with the process of the following (E) further.
- E) From the chlorosilane distillate residue after separation of the electronic material grade chlorosilanes in the purification step of (C), the aldehyde compound and a fraction containing chlorosilanes as main components are separated, and the aldehyde A high-boiling substance separation step in which a fraction mainly composed of a compound and chlorosilanes is supplied to the impurity conversion step (B) as at least a part of the aldehyde compound:
- the chlorosilane distillate obtained in the hydrogenation step or the chlorination step (A) is a first chlorosilane distillate mainly composed of trichlorosilane and a fraction having a boiling point lower than that of trichlorosilane.
- the product is separated into tetrachlorosilane and a second class chlorosilane distillate mainly composed of tetrachlorosilane and a fraction having a boiling point higher than that of tetrachlorosilane.
- the first class chlorosilane distillate is further separated into a distillate mainly composed of trichlorosilane and a distillate mainly composed of a fraction having a boiling point lower than that of trichlorosilane. And supplying the distillate containing trichlorosilane as a main component to the impurity conversion step (B):
- step (H) may be further provided.
- the chlorosilanes distillate obtained in the hydrogenation step or chlorination step of (A) above is a third class chlorosilane distillate mainly composed of a fraction having a boiling point lower than that of trichlorosilane.
- the fourth class chlorosilane distillate is further separated into a distillate mainly composed of trichlorosilane and a distillate mainly composed of a fraction having a boiling point higher than that of trichlorosilane. And supplying the distillate containing trichlorosilane as a main component to the impurity conversion step (B):
- the treatment temperature in the impurity conversion step (B) is 0 ° C. or higher and 150 ° C. or lower.
- Examples of the aldehyde compound represented by the general formula Ar—R—CHO include those represented by the following structural formula.
- Ar is a substituted or unsubstituted aryl group
- R1 and R2 are hydrogen or a hydrocarbon group having 1 to 20 carbon atoms.
- the aldehyde compound represented by the structural formula is, for example, a cinnamaldehyde derivative.
- cinnamaldehyde derivatives examples include cinnamaldehyde, ⁇ -methylcinnamaldehyde, ⁇ -pentylcinnamaldehyde, ⁇ -hexylcinnamaldehyde, p-isopropyl- ⁇ -methylhydrocinnamaldehyde, p-tert-butyl- ⁇ -methylhydrocinna
- An example is mualdehyde.
- the electronic material grade chlorosilanes purified by the present invention include, for example, polycrystalline silicon production for semiconductor use, polycrystalline silicon production for solar cell use, silicon oxide film formation, polycrystalline silicon film formation, silicon compound It is useful as a raw material for either thin film deposition or epitaxial wafer production.
- the method for purifying chlorosilanes according to the present invention includes at least three steps of a hydrogenation step and / or a chlorination step, an impurity conversion step, and a purification step.
- an aldehyde compound represented by the general formula Ar—R—CHO Ar is a substituted or unsubstituted aryl group, R is an organic group having 2 or more carbon atoms
- Ar is a substituted or unsubstituted aryl group, R is an organic group having 2 or more carbon atoms
- the donor impurities and acceptor impurities that have been converted are converted into high-boiling substances.
- the chlorosilane distillate after the donor impurity and the acceptor impurity are converted into high-boiling substances is sent to the purification step.
- the purification step by using a distillation column or the like, high purity chlorosilanes from which donor impurities and acceptor impurities are sufficiently removed are obtained from the top of the column and recovered
- the technology based on the purification method of chlorosilanes having such a configuration does not have problems such as easy handling and complicated waste disposal. Moreover, an apparatus such as an adsorption tower is not required, and the facilities are not complicated. That is, the problem of the conventional method is solved.
- FIG. 1 It is a block diagram for demonstrating one aspect
- FIG. It is a block diagram for demonstrating the other aspect of the purification method of chlorosilanes of this invention.
- a hydrogenation step in which chlorosilanes mainly containing tetrachlorosilane and hydrogen are reacted in the presence of metal grade silicon to obtain a chlorosilane distillate containing trichlorosilane, or metal grade silicon and hydrogen chloride are reacted.
- Examples of the aldehyde compound represented by the general formula Ar—R—CHO include those represented by the following structural formula.
- Ar is a substituted or unsubstituted aryl group
- R1 and R2 are hydrogen or a hydrocarbon group having 1 to 20 carbon atoms.
- the aldehyde compound represented by the above structural formula is, for example, a cinnamaldehyde derivative such as cinnamaldehyde, ⁇ -methylcinnamaldehyde, ⁇ -pentylcinnamaldehyde, ⁇ -hexylcinnamaldehyde, p-isopropyl- ⁇ -methylhydrocinna
- a cinnamaldehyde derivative such as cinnamaldehyde, ⁇ -methylcinnamaldehyde, ⁇ -pentylcinnamaldehyde, ⁇ -hexylcinnamaldehyde, p-isopropyl- ⁇ -methylhydrocinna
- An example is mualdehyde, p-tert-butyl- ⁇ -methylhydrocinnamaldehyde.
- the aldehyde compound represented by Ar—R—CHO described above is chlorinated in the presence of a metal chloride such as iron chloride, as in the case of benzaldehydes.
- a metal chloride such as iron chloride
- cinnamaldehyde is chlorinated by the reaction shown in the following formula.
- the donor impurity and acceptor impurity remover contained in the chlorosilane distillate is a compound containing an aldehyde group, and the aldehyde part in the compound is chlorine. It is preferable that the substance does not become highly polymerized by causing an intramolecular reaction even when it is made into a polymer.
- the aldehyde compound represented by Ar—R—CHO described above is characterized by having an organic group having 2 or more carbon atoms between the aryl group and the aldehyde group.
- Ar—R—CHO since the aldehyde compound represented by the general formula Ar—R—CHO has an organic group represented by R, it can form an intramolecular reaction with a benzene ring, making it difficult to form a highly polymerized product. It is thought that shows.
- FIG. 1 is a block diagram for explaining one embodiment of the method for purifying chlorosilanes of the present invention.
- the method for purifying chlorosilanes shown in this figure includes at least three steps of a hydrogenation step 101 and / or a chlorination step 102, an impurity conversion step 103, and a purification step 104.
- the hydrogenation step 101 and the chlorination step 102 may be provided with only one or both according to the request of the system.
- chlorosilanes mainly composed of metallic silicon and tetrachlorosilane and hydrogen are supplied to obtain crude chlorosilanes containing trichlorosilane.
- metal silicon and hydrogen chloride are supplied, and crude chlorosilanes containing trichlorosilane are obtained in the presence of a catalyst.
- Crude chlorosilanes obtained in the hydrogenation step 101 or chlorination step 102 are purified as necessary, and then chlorosilanes distillate containing chlorosilanes such as dichlorosilane, trichlorosilane, and tetrachlorosilane as main components.
- chlorosilanes such as dichlorosilane, trichlorosilane, and tetrachlorosilane as main components.
- impurity conversion step 103 To the impurity conversion step 103.
- the aldehyde compound represented by the general formula Ar—R—CHO described above is added, and the donor impurity and the acceptor impurity contained in the chlorosilane distillate are converted into high-boiling substances.
- the amount of the aldehyde compound supplied (added) to the impurity conversion step 103 is preferably not less than the stoichiometric amount of donor impurities and acceptor impurities contained in the chlorosilane distillate.
- the amount of the aldehyde compound supplied in the impurity conversion step 103 is equal to or more than the molar amount of the donor impurity and acceptor impurity contained in the chlorosilane distillate, and is economically reasonable. For example, from the amount of impurities generally contained, 20% by mass or less is sufficient with respect to the chlorosilane distillate to be treated.
- Chlorosilanes after conversion of donor impurities and acceptor impurities contained in the chlorosilanes distillate into high-boiling compounds by treatment in the presence of an aldehyde compound represented by the general formula Ar—R—CHO
- the distillate is sent to the purification step 104.
- chlorosilanes distillate sent to the purification step 104 in addition to chlorosilanes containing trichlorosilane, an excess of the aldehyde compound added in the impurity conversion step 103, conversion of donor impurities and acceptor impurities occurred. Contains high boilers.
- a distillation tower or the like is used to separate and purify chlorosilanes mainly composed of trichlorosilane.
- the contents of the chlorosilane distillate sent from the impurity conversion step 103 are chlorosilanes and high-boiling products of aldehyde compounds, donor impurities and acceptor impurities represented by the general formula Ar—R—CHO. Therefore, by using a distillation column or the like, chlorosilanes that are easily recovered from the system from the top of the column and purified can be obtained.
- the obtained chlorosilanes are high-purity chlorosilanes from which donor impurities and acceptor impurities have been sufficiently removed, and are sufficiently high as raw material chlorosilanes for producing semiconductor grade high-purity polycrystalline silicon and the like. It is of purity (electronic material grade).
- the residual liquid after separation of the purified chlorosilanes in the purification step 104 is discharged from the bottom of the distillation column, etc., and in this residual liquid, the chlorosilanes, the general formula Ar— High-boiling substances of aldehyde compounds represented by R—CHO, donor impurities, and acceptor impurities are included. Of these, chlorosilanes and aldehyde compounds represented by the general formula Ar—R—CHO can be reused again in the impurity conversion step 103.
- FIG. 2 is a block diagram showing an embodiment in which the residual liquid after separation of the purified chlorosilanes in the purification step 104 is reused in the impurity conversion step 103.
- an electronic material grade At least a portion of the chlorosilane distillate residue after separation of the chlorosilanes is supplied to the impurity conversion step 103 as at least a portion of the aldehyde compound described above (distillate residue supply step). If such re-use is performed, the amount of aldehyde compounds supplied from the outside is equivalent to the amount of aldehyde compounds to be re-supplied to the separation step 103 in addition to the effective use of chlorosilanes in the residual liquid. Can be reduced.
- the chlorosilane distillate residual liquid after separating the electronic material grade chlorosilanes in the purification process 104 in advance.
- Separating the above-mentioned fraction containing aldehyde compound and chlorosilane as main components and supplying the fraction containing aldehyde compound and chlorosilane as main components to impurity conversion step 103 as at least part of the aldehyde compound A material separation step 201 may be provided.
- a distillation column or the like may be used for such a high boiling point separation step 201.
- the residual liquid mainly composed of high-boiling substances obtained by separating a fraction mainly composed of aldehyde compounds and chlorosilanes as described above contains unnecessary donor impurities and acceptor impurities high-boiling substances. Useful materials can be recovered while partially removing unnecessary materials.
- FIGSecond Embodiment 4 to 9 are block diagrams for explaining other aspects of the purification method of chlorosilanes of the present invention.
- the steps included in the first embodiment are shown.
- at least one of a high boiling fraction separation step 301 and a low boiling fraction separation step 302 is provided.
- the high-boiling fraction separation step 301 is a first step in which the chlorosilane distillate obtained in the hydrogenation step 101 or the chlorination step 102 is composed mainly of trichlorosilane and a fraction having a lower boiling point than trichlorosilane.
- the first chlorosilane distillate is separated into the first chlorosilane distillate and the second chlorosilane distillate mainly composed of tetrachlorosilane and a fraction having a higher boiling point than tetrachlorosilane.
- the low-boiling fraction separation step 302 is a third class chlorosilane whose main component is a fraction having a boiling point lower than that of trichlorosilane, obtained from the hydrogenation step 101 or the chlorination step 102.
- the distillate is separated into trichlorosilane and a fourth class chlorosilane distillate mainly composed of trichlorosilane and a fraction having a higher boiling point than trichlorosilane, and the fourth class chlorosilane distillate is converted into impurities.
- This is a step of supplying the high-boiling fraction separating step separately provided before the step 103 or the impurity conversion step.
- the chlorosilane distillate containing trichlorosilane produced in the hydrogenation step 101 and / or the chlorination step 102 is purified by the high boiling point distillate separation step 301 to be contained in the chlorosilane distillate. After the concentration of trichlorosilane is increased, it is sent to the impurity conversion step 103.
- dichlorosilane, trichlorosilane, tetrachlorosilane, impurities having a lower boiling point than dichlorosilane and impurities having a higher boiling point than tetrachlorosilane are included. It is mixed.
- the impurities This is advantageous from the viewpoint of refining the raw material for producing polycrystalline silicon, such as reducing the equipment load of the conversion step 103.
- a chlorosilane distillate containing trichlorosilane sent from the hydrogenation step 101 or the chlorination step 102 is converted into a fraction having a lower boiling point than trichlorosilane and trichlorosilane.
- Chlorosilanes having a main component for convenience, referred to as “first class chlorosilane distillate”
- tetrachlorosilane and a fraction having a higher boiling point than tetrachlorosilane for convenience, “second class of chlorosilanes”. Chlorosilanes distillate ").
- a distillation column or the like can be used.
- the first chlorosilane distillate is extracted from the top of the column, and the second chlorosilane distillate is extracted from the bottom of the column.
- chlorosilanes first class chlorosilane distillate
- chlorosilanes mainly composed of trichlorosilane and a fraction having a boiling point lower than that of trichlorosilane are sent to the impurity conversion step 103.
- the chlorosilane distillate containing trichlorosilane produced in the hydrogenation step 101 and / or the chlorination step 102 is purified by the low boiling point distillate separation step 302 to obtain a chlorosilane distillate. It may be sent to the impurity conversion step 103 after increasing the concentration of trichlorosilane in the product.
- a chlorosilane distillate containing trichlorosilane sent from the hydrogenation step 101 or the chlorination step 102 is composed mainly of a fraction having a lower boiling point than trichlorosilane.
- Chlorosilanes for convenience, referred to as “the third class chlorosilane distillate”
- chlorosilanes having a higher boiling point than trichlorosilane and trichlorosilane for convenience, “the fourth class chlorosilanes”. Distillate ").
- a distillation column or the like can be used.
- the third chlorosilane distillate is extracted from the top of the column, and the fourth chlorosilane distillate is extracted from the bottom of the column.
- trichlorosilane and chlorosilanes having a higher boiling point than trichlorosilane are sent to the impurity conversion step 103.
- chlorosilanes first class chlorosilanes fractions mainly composed of trichlorosilane and a fraction having a boiling point lower than that of trichlorosilane obtained in the high-boiling fraction separation step 301 are used.
- the product is further treated in a low boiling fraction separation step 302 to separate chlorosilanes such as dichlorosilane having a lower boiling point than trichlorosilane, thereby further increasing the concentration of trichlorosilane to the impurity conversion step 103. It may be sent to.
- a low boiling point fraction separation step 302 is provided first, and chlorosilane containing a fraction having a lower boiling point than trichlorosilane as a main component. Chlorosilanes after separation of chlorosilanes (distillation product of type 3 chlorosilanes) is sent to a high-boiling fraction separation step 301 and chlorosilanes mainly composed of tetrachlorosilane and a fraction having a boiling point higher than tetrachlorosilane ( The second type chlorosilane distillate) may be separated.
- the residual liquid after separation of the purified chlorosilanes in the purification step 104 is reused in the impurity conversion step 103.
- at least a portion of the chlorosilane distillate residue after separation of the electronic material grade chlorosilanes in the purification step 104 is supplied to the impurity conversion step 103 as at least a portion of the aldehyde compound described above. .
- the chlorosilanes after separation of the electronic material grade chlorosilanes in the purification step 104 in advance.
- the distillate residue is separated into the above-mentioned fractions mainly composed of aldehyde compounds and chlorosilanes and the fractions mainly composed of high-boiling substances, and the former (distillates mainly composed of aldehyde compounds and chlorosilanes).
- a high boiling point substance separation step 201 is provided for supplying the component to the impurity conversion step 103 as at least part of the aldehyde compound.
- Example 1 At room temperature of 20-30 ° C, 7,006 g of chlorosilane distillate containing trichlorosilane as a main component was charged in a sample container, 27 g of cinnamaldehyde was added, and after stirring for 1 hour, boron in the chlorosilane solution The concentration of phosphorus was measured.
- the boron content in the chlorosilane solution before cinnamaldehyde was charged was 11.5 ppba and the phosphorus content was 0.2 ppba.
- the amount of boron in the chlorosilane solution after stirring was 1.0 ppba, and the amount of phosphorus was 0.14 ppba.
- the mixed solution of the cinnamaldehyde and the chlorosilane solution after the stirring was sufficiently evaporated at a normal pressure by nitrogen aeration. The evaporation residue could be easily discharged from the container, and the residue was a liquid mainly composed of cinnamaldehyde.
- the boron content in the chlorosilane solution after stirring was 0.8 ppba, and the phosphorus content was 0.1 ppba.
- the mixed solution of the benzaldehyde and the chlorosilane solution after the stirring was sufficiently evaporated by aeration of nitrogen at normal pressure. The evaporation residue could not be discharged from the container. When the container was opened and the evaporation residue was observed, it was a black solid.
- Examples 2 to 4 Under the same conditions as in Example 1, the aldehyde compounds shown in Table 1 were added instead of cinnamaldehyde.
- a chlorosilane distillate containing trichlorosilane as a main component was charged into a sample container at room temperature of 20 to 30 ° C.
- the chlorosilane distillate charged is the same stock solution used in Example 1.
- Each aldehyde compound was added to the chlorosilane distillate charged so as to have the same number of moles of cinnamaldehyde as used in Experimental Example 1. After stirring for 1 hour, the concentrations of boron and phosphorus in the chlorosilane solution were measured.
- Table 1 shows the amounts of boron and phosphorus in the chlorosilane solution after stirring.
- the mixed solution of each aldehyde compound and the chlorosilane solution after stirring was sufficiently evaporated by aeration of nitrogen at normal pressure.
- the evaporation residue could be easily discharged from the container, and the residue was a liquid mainly composed of each aldehyde compound.
- Example 5 Purification of chlorosilanes was performed using the equipment shown in the block diagram of FIG. Addition of ⁇ -methylcinnamaldehyde in impurity conversion step 103 to the chlorosilane distillate mixture containing 70% trichlorosilane and 30% tetrachlorosilane, so that the amount is 1,000 times the molar amount of boron in the mixture. did.
- the chlorosilane distillate to which ⁇ -methylcinnamaldehyde was added was sent to the purification step 104 and separated in a distillation column. Purified chlorosilanes mainly composed of trichlorosilane were obtained from the top of the distillation column.
- Polysilicon was produced from purified chlorosilanes and its resistivity was measured.
- the resistivity of the N-type was 3,500 ⁇ cm, which was high.
- the residual liquid discharged from the bottom of the distillation column in the purification step 104 was separated into ⁇ -methylcinnamaldehyde in the high boiling point separation step 201 and re-supplied to the impurity conversion step 103.
- the electronic material grade chlorosilanes obtained by the present invention are not only useful for producing polycrystalline silicon for semiconductor applications, but also for producing polycrystalline silicon for solar cells, forming silicon oxide films, forming polycrystalline silicon films. It is also useful as a raw material for film formation, silicon compound thin film formation, or epitaxial wafer production.
- the present invention provides a technique for removing donor impurities and acceptor impurities from a chlorosilane distillate to reduce the content.
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Abstract
Description
そして、ドナー不純物およびアクセプタ不純物の除去が不充分なクロロシラン類を原料として多結晶シリコンを製造すると、所望の特性の多結晶シリコンが得られない結果となる。
(A)金属グレードシリコンの存在下でテトラクロロシランを主成分とするクロロシラン類と水素を反応させてトリクロロシランを含むクロロシラン類留出物を得る水素化工程;または、
金属グレードシリコンと塩化水素を反応させてトリクロロシランを含むクロロシラン類留出物を得る塩素化工程:
(B)前記(A)の水素化工程または塩素化工程で得られたクロロシラン類留出物を一般式Ar-R-CHOで表記されるアルデヒド化合物の存在下で処理して、前記クロロシラン類留出物中に含有されているドナー不純物およびアクセプタ不純物を高沸点物に転化させる不純物転化工程(ここで、上記一般式中、Arは置換または未置換のアリール基であり、Rは炭素数2以上の有機基である):
(C)前記不純物転化工程を経たクロロシラン類留出物から電子材料グレードクロロシラン類を分離して系外に回収する精製工程:
(D)前記(C)の精製工程で電子材料グレードクロロシラン類を分離した後のクロロシラン類留出物残液の少なくとも一部を、前記アルデヒド化合物の少なくとも一部として前記(B)の不純物転化工程に供給する留出物残液供給工程:
(E)前記(C)の精製工程で電子材料グレードクロロシラン類を分離した後のクロロシラン類留出物残液より、前記アルデヒド化合物とクロロシラン類を主成分とする留分を分離して、前記アルデヒド化合物とクロロシラン類を主成分とする留分を、前記アルデヒド化合物の少なくとも一部として前記(B)の不純物転化工程に供給する高沸点物分離工程:
(F)前記(A)の水素化工程または塩素化工程で得られたクロロシラン類留出物を、トリクロロシランおよびトリクロロシランよりも低沸点の留分を主成分とする第1類のクロロシラン類留出物と、テトラクロロシランおよびテトラクロロシランよりも高沸点の留分を主成分とする第2類のクロロシラン類留出物とに分離し、前記第1類のクロロシラン類留出物を、前記(B)の不純物転化工程に供給する高沸点留分分離工程:
(G)前記第1類のクロロシラン類留出物を、さらに、トリクロロシランを主成分とする留出物と、トリクロロシランよりも低沸点の留分を主成分とする留出物とに分離し、前記トリクロロシランを主成分とする留出物を、前記(B)の不純物転化工程に供給する工程:
(H)前記(A)の水素化工程または塩素化工程で得られたクロロシラン類留出物を、トリクロロシランよりも低沸点の留分を主成分とする第3類のクロロシラン類留出物と、トリクロロシランおよびトリクロロシランよりも高沸点の留分を主成分とする第4類のクロロシラン類留出物とに分離し、前記第4類のクロロシラン類留出物を、前記(B)の不純物転化工程に供給する低沸点留分分離工程:
(I)前記第4類のクロロシラン類留出物を、さらに、トリクロロシランを主成分とする留出物と、トリクロロシランよりも高沸点の留分を主成分とする留出物とに分離し、前記トリクロロシランを主成分とする留出物を、前記(B)の不純物転化工程に供給する工程:
図1は、本発明のクロロシラン類の精製方法の一態様を説明するためのブロック図である。この図に示したクロロシラン類の精製方法は、水素化工程101および/または塩素化工程102、不純物転化工程103、精製工程104の少なくとも3つの工程を備えている。水素化工程101と塩素化工程102はシステムの要請により一方のみを備えるものでもよく、両方を備えるものでもよい。
図4~図9は、本発明のクロロシラン類の精製方法の他の態様を説明するためのブロック図で、これらの図に示したクロロシラン類の精製方法では、第1の実施態様が備える工程に加え、高沸点留分分離工程301および低沸点留分分離工程302の少なくとも一方の工程が設けられている。
20~30℃の室温条件にて、サンプル容器にトリクロロシランを主成分とするクロロシラン類留出物を7,006g仕込んだ後にシンナムアルデヒドを27g添加し、1時間撹拌後、クロロシラン類溶液中のボロンとリンの濃度を測定した。
実施例1と同様の条件で、シンナムアルデヒドのかわりにベンズアルデヒドを添加して行った。20~30℃の室温条件にて、サンプル容器にトリクロロシランを主成分とするクロロシラン類留出物を6,988g仕込んだ。仕込んだクロロシラン類留出物は、実施例1で用いたものと同じ原液である。仕込んだクロロシラン類留出物に、実験例1で用いたシンナムアルデヒドのモル数と同じになるように、ベンズアルデヒドを22g添加した。1時間撹拌後、クロロシラン類溶液中のボロンとリンの濃度を測定した。
実施例1と同様の条件で、シンナムアルデヒドのかわりに表1に示すアルデヒド化合物を添加して行った。20~30℃の室温条件にて、サンプル容器にトリクロロシランを主成分とするクロロシラン類留出物を仕込んだ。仕込んだクロロシラン類留出物は、実施例1で用いたものと同じ原液である。仕込んだクロロシラン類留出物に、実験例1で用いたシンナムアルデヒドのモル数と同じになるように、各アルデヒド化合物を添加した。1時間撹拌後、クロロシラン類溶液中のボロンとリンの濃度を測定した。撹拌後のクロロシラン類溶液中のボロン量とリン量を、表1に示す。撹拌後の各アルデヒド化合物とクロロシラン類溶液の混合液を、常圧で窒素通気にて十分蒸発させた。蒸発残分は容器より容易に排出することができ、残分は各アルデヒド化合物を主成分とする液体であった。
図3のブロック図に示した設備により、クロロシラン類の精製を実施した。トリクロロシランが70%、テトラクロロシランが30%のクロロシラン類留出物混合液に、混合液中のボロン量のモル基準で1,000倍になるよう、不純物転化工程103にてα-メチルシンナムアルデヒドを添加した。α-メチルシンナムアルデヒドが添加されたクロロシラン類留出物は精製工程104に送られ、蒸留塔にて分離を行った。蒸留塔の塔頂部より、トリクロロシランを主成分とする精製されたクロロシラン類を得た。精製されたクロロシラン類を原料にポリシリコンを製造してその抵抗率を測定したところ、N型で3,500Ωcmと高抵抗であった。精製工程104の蒸留塔の塔底部より排出された残液は、高沸点物分離工程201にてα-メチルシンナムアルデヒドを分離し、不純物転化工程103に再供給した。
102 塩素化工程
103 不純物転化工程
104 精製工程
201 高沸点物分離工程
301 高沸点留分分離工程
302 低沸点留分分離工程
Claims (13)
- 下記の(A)~(C)の工程を備えていることを特徴とするクロロシラン類の精製方法。
(A)金属グレードシリコンの存在下でテトラクロロシランを主成分とするクロロシラン類と水素を反応させてトリクロロシランを含むクロロシラン類留出物を得る水素化工程;または、
金属グレードシリコンと塩化水素を反応させてトリクロロシランを含むクロロシラン類留出物を得る塩素化工程:
(B)前記(A)の水素化工程または塩素化工程で得られたクロロシラン類留出物を一般式Ar-R-CHOで表記されるアルデヒド化合物の存在下で処理して、前記クロロシラン類留出物中に含有されているドナー不純物およびアクセプタ不純物を高沸点物に転化させる不純物転化工程(ここで、上記一般式中、Arは置換または未置換のアリール基であり、Rは炭素数2以上の有機基である):
(C)前記不純物転化工程を経たクロロシラン類留出物から電子材料グレードクロロシラン類を分離して系外に回収する精製工程: - 更に、下記の(D)の工程を備えている請求項1に記載のクロロシラン類の精製方法。
(D)前記(C)の精製工程で電子材料グレードクロロシラン類を分離した後のクロロシラン類留出物残液の少なくとも一部を、前記アルデヒド化合物の少なくとも一部として前記(B)の不純物転化工程に供給する留出物残液供給工程: - 更に、下記の(E)の工程を備えている請求項1に記載のクロロシラン類の精製方法。
(E)前記(C)の精製工程で電子材料グレードクロロシラン類を分離した後のクロロシラン類留出物残液より、前記アルデヒド化合物とクロロシラン類を主成分とする留分を分離して、前記アルデヒド化合物とクロロシラン類を主成分とする留分を、前記アルデヒド化合物の少なくとも一部として前記(B)の不純物転化工程に供給する高沸点物分離工程: - 更に、下記の(F)の工程を備えている請求項1乃至3の何れか1項に記載のクロロシラン類の精製方法。
(F)前記(A)の水素化工程または塩素化工程で得られたクロロシラン類留出物を、トリクロロシランおよびトリクロロシランよりも低沸点の留分を主成分とする第1類のクロロシラン類留出物と、テトラクロロシランおよびテトラクロロシランよりも高沸点の留分を主成分とする第2類のクロロシラン類留出物とに分離し、前記第1類のクロロシラン類留出物を、前記(B)の不純物転化工程に供給する高沸点留分分離工程: - 更に、下記の(G)の工程を備えている請求項4に記載のクロロシラン類の精製方法。
(G)前記第1類のクロロシラン類留出物を、さらに、トリクロロシランを主成分とする留出物と、トリクロロシランよりも低沸点の留分を主成分とする留出物とに分離し、前記トリクロロシランを主成分とする留出物を、前記(B)の不純物転化工程に供給する工程: - 更に、下記の(H)の工程を備えている請求項1乃至3の何れか1項に記載のクロロシラン類の精製方法。
(H)前記(A)の水素化工程または塩素化工程で得られたクロロシラン類留出物を、トリクロロシランよりも低沸点の留分を主成分とする第3類のクロロシラン類留出物と、トリクロロシランおよびトリクロロシランよりも高沸点の留分を主成分とする第4類のクロロシラン類留出物とに分離し、前記第4類のクロロシラン類留出物を、前記(B)の不純物転化工程に供給する低沸点留分分離工程: - 更に、下記の(I)の工程を備えている請求項6に記載のクロロシラン類の精製方法。
(I)前記第4類のクロロシラン類留出物を、さらに、トリクロロシランを主成分とする留出物と、トリクロロシランよりも高沸点の留分を主成分とする留出物とに分離し、前記トリクロロシランを主成分とする留出物を、前記(B)の不純物転化工程に供給する工程: - 前記(B)の不純物転化工程の処理温度は0℃以上150℃以下である、請求項1に記載のクロロシラン類の精製方法。
- 前記(B)の不純物転化工程は、前記一般式Ar-R-CHOで表記されるアルデヒド化合物を、前記クロロシラン類留出物中に含有されているドナー不純物およびアクセプタ不純物の化学量論量以上に添加して行われる、請求項1に記載のクロロシラン類の精製方法。
- 前記構造式で示されるアルデヒド化合物が、シンナムアルデヒド誘導体である請求項10に記載のクロロシラン類の精製方法。
- 前記シンナムアルデヒド誘導体が、シンナムアルデヒド、α-メチルシンナムアルデヒド、α-ペンチルシンナムアルデヒド、α-ヘキシルシンナムアルデヒド、p-イソプロピル-α-メチルヒドロシンナムアルデヒド、p-tert-ブチル-α-メチルヒドロシンナムアルデヒドの何れかである請求項11に記載のクロロシラン類の精製方法。
- 前記電子材料グレードクロロシラン類は、半導体用途の多結晶シリコン製造、太陽電池用途の多結晶シリコン製造、シリコン酸化膜の成膜、多結晶シリコン膜の成膜、シリコン化合物薄膜の成膜、エピタキシャルウェハ製造の何れかを目的とした原料として用いられるものである、請求項1に記載のクロロシラン類の精製方法。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013001632A (ja) * | 2011-06-21 | 2013-01-07 | Shin-Etsu Chemical Co Ltd | クロロシラン類の精製方法 |
EP2957543A4 (en) * | 2013-02-13 | 2016-08-10 | Shinetsu Chemical Co | PROCESS FOR THE PREPARATION OF TRICHLOROSILANE |
CN110402236A (zh) * | 2016-12-15 | 2019-11-01 | 因诺沃赫姆企业家有限公司 | 通过分步结晶提高低聚硅烷和低聚硅烷化合物纯度的方法 |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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JP6069167B2 (ja) * | 2013-10-23 | 2017-02-01 | 信越化学工業株式会社 | 多結晶シリコンの製造方法 |
US10584035B2 (en) | 2017-02-24 | 2020-03-10 | Shin-Etsu Chemical Co., Ltd. | Purification system of trichlorosilane and silicon crystal |
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DE102017125221A1 (de) * | 2017-10-27 | 2019-05-02 | Nexwafe Gmbh | Verfahren und Vorrichtung zur Entfernung von Verunreinigungen aus Chlorsilanen |
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EP3885315A4 (en) * | 2018-12-27 | 2022-08-17 | Tokuyama Corporation | MANUFACTURING PROCESS FOR CHLORSILANE |
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KR20210149714A (ko) | 2019-04-05 | 2021-12-09 | 가부시키가이샤 도쿠야마 | 다결정 실리콘 원료 |
JPWO2020204143A1 (ja) | 2019-04-05 | 2020-10-08 | ||
CN116715242B (zh) * | 2023-05-31 | 2024-02-02 | 宁夏润阳硅材料科技有限公司 | 一种还原工艺用氢气中碳杂质含量控制方法及系统 |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2821460A (en) | 1955-08-31 | 1958-01-28 | Bell Telephone Labor Inc | Method of purifying silicon tetrachloride and germanium tetrachloride |
US3126248A (en) | 1964-03-24 | Process for producing purified | ||
US3252752A (en) | 1958-01-11 | 1966-05-24 | Licentia Gmbh | Method for producing pure silane and chlorinated silanes |
DE1289834B (de) | 1960-08-11 | 1969-02-27 | Haldor Frederik Axel Dipl Ing | Verfahren zur Reinigung einer anorganischen Halogenidverbindung oder einer Mischung solcher Halogenidverbindungen |
US4112057A (en) | 1975-10-20 | 1978-09-05 | Wacker-Chemitronic Gesellschaft Fur Elektronik-Grundstoffe Mbh | Process for purifying halogenosilanes |
JPS5734012A (en) * | 1980-07-29 | 1982-02-24 | Shin Etsu Chem Co Ltd | Purifying method of chlorosilane |
JPS58500895A (ja) | 1981-06-15 | 1983-06-02 | モトロ−ラ・インコ−ポレ−テツド | シリコン原材料の精製法 |
JPS58161915A (ja) | 1982-03-17 | 1983-09-26 | Shin Etsu Chem Co Ltd | トリクロロシランの製造方法 |
JPS58217422A (ja) | 1982-03-31 | 1983-12-17 | ユニオン・カ−バイド・コ−ポレ−シヨン | 高純度シランの製造方法 |
JPH04300206A (ja) | 1991-03-28 | 1992-10-23 | Osaka Titanium Co Ltd | シリコン塩化物の精製方法 |
JP2001002407A (ja) | 1999-06-17 | 2001-01-09 | Shin Etsu Chem Co Ltd | クロロシラン類中のボロン化合物の分離方法及びクロロシラン類蒸発用組成物 |
JP2005067979A (ja) | 2003-08-27 | 2005-03-17 | Tokuyama Corp | クロロシラン類の精製方法 |
JP2008532907A (ja) | 2005-03-09 | 2008-08-21 | アールイーシー シリコン インコーポレイテッド | ヒドロクロロシランの製造方法 |
JP2009062213A (ja) | 2007-09-05 | 2009-03-26 | Shin Etsu Chem Co Ltd | クロロシラン類の精製方法 |
Family Cites Families (1)
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JP4714197B2 (ja) * | 2007-09-05 | 2011-06-29 | 信越化学工業株式会社 | トリクロロシランの製造方法および多結晶シリコンの製造方法 |
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Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3126248A (en) | 1964-03-24 | Process for producing purified | ||
US2821460A (en) | 1955-08-31 | 1958-01-28 | Bell Telephone Labor Inc | Method of purifying silicon tetrachloride and germanium tetrachloride |
US3252752A (en) | 1958-01-11 | 1966-05-24 | Licentia Gmbh | Method for producing pure silane and chlorinated silanes |
DE1289834B (de) | 1960-08-11 | 1969-02-27 | Haldor Frederik Axel Dipl Ing | Verfahren zur Reinigung einer anorganischen Halogenidverbindung oder einer Mischung solcher Halogenidverbindungen |
US4112057A (en) | 1975-10-20 | 1978-09-05 | Wacker-Chemitronic Gesellschaft Fur Elektronik-Grundstoffe Mbh | Process for purifying halogenosilanes |
JPS5734012A (en) * | 1980-07-29 | 1982-02-24 | Shin Etsu Chem Co Ltd | Purifying method of chlorosilane |
JPS58500895A (ja) | 1981-06-15 | 1983-06-02 | モトロ−ラ・インコ−ポレ−テツド | シリコン原材料の精製法 |
JPS58161915A (ja) | 1982-03-17 | 1983-09-26 | Shin Etsu Chem Co Ltd | トリクロロシランの製造方法 |
JPS58217422A (ja) | 1982-03-31 | 1983-12-17 | ユニオン・カ−バイド・コ−ポレ−シヨン | 高純度シランの製造方法 |
JPH04300206A (ja) | 1991-03-28 | 1992-10-23 | Osaka Titanium Co Ltd | シリコン塩化物の精製方法 |
JP2001002407A (ja) | 1999-06-17 | 2001-01-09 | Shin Etsu Chem Co Ltd | クロロシラン類中のボロン化合物の分離方法及びクロロシラン類蒸発用組成物 |
JP2005067979A (ja) | 2003-08-27 | 2005-03-17 | Tokuyama Corp | クロロシラン類の精製方法 |
JP2008532907A (ja) | 2005-03-09 | 2008-08-21 | アールイーシー シリコン インコーポレイテッド | ヒドロクロロシランの製造方法 |
JP2009062213A (ja) | 2007-09-05 | 2009-03-26 | Shin Etsu Chem Co Ltd | クロロシラン類の精製方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013001632A (ja) * | 2011-06-21 | 2013-01-07 | Shin-Etsu Chemical Co Ltd | クロロシラン類の精製方法 |
EP2957543A4 (en) * | 2013-02-13 | 2016-08-10 | Shinetsu Chemical Co | PROCESS FOR THE PREPARATION OF TRICHLOROSILANE |
CN110402236A (zh) * | 2016-12-15 | 2019-11-01 | 因诺沃赫姆企业家有限公司 | 通过分步结晶提高低聚硅烷和低聚硅烷化合物纯度的方法 |
CN110402236B (zh) * | 2016-12-15 | 2023-04-04 | Psc聚硅烷化学有限公司 | 通过分步结晶提高低聚硅烷和低聚硅烷化合物纯度的方法 |
Also Published As
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JP2012091960A (ja) | 2012-05-17 |
US20130177492A1 (en) | 2013-07-11 |
EP2634142A1 (en) | 2013-09-04 |
CN103201218A (zh) | 2013-07-10 |
EP2634142B1 (en) | 2017-07-05 |
JP5542026B2 (ja) | 2014-07-09 |
CN103201218B (zh) | 2015-10-07 |
EP2634142A4 (en) | 2014-11-05 |
US9126838B2 (en) | 2015-09-08 |
AU2011322027A1 (en) | 2013-03-21 |
AU2011322027B2 (en) | 2013-12-05 |
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