CN101189245B - Process for the production of hydrochlorosilanes - Google Patents

Process for the production of hydrochlorosilanes Download PDF

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CN101189245B
CN101189245B CN2005800497460A CN200580049746A CN101189245B CN 101189245 B CN101189245 B CN 101189245B CN 2005800497460 A CN2005800497460 A CN 2005800497460A CN 200580049746 A CN200580049746 A CN 200580049746A CN 101189245 B CN101189245 B CN 101189245B
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silicon
hydrogen
promoter metals
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oxide
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CN101189245A (en
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威廉·C·布勒内曼
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Rec Silicon Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/122—Halides of copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Hydrogen-containing chlorosilanes are prepared by reacting hydrogen with silicon tetrachloride and/or hydrogen chloride and silicon wherein the surface of the silicon has been modified by a chemical vapor deposition of one or more catalytic materials, such as copper.

Description

The method for preparing silicon hydride chlorid
Technical field
The present invention relates to a kind of method for preparing hydrogenous chlorosilane, particularly Trichloromonosilane and dichlorosilane by silicon.
Background technology
Known under the condition of not using catalyzer or promotor (Ingle, US 4526769), through being reacted, silicon tetrachloride and hydrogen and silicon prepares Trichloromonosilane.Entire reaction course can be represented with following formula:
3SiCl 4+2H 2+Si→4HSiCl 3 (1)
Also known under the condition of not using catalyzer, through hydrogenchloride and silicon being reacted prepare the method for Trichloromonosilane, can be expressed from the next:
3HCl+Si→HSiCl 3+H 2 (2)
Also known, if use for example copper (Breneman, US 4676967) of some metal, can increase the speed of said reaction and can improve the selectivity of said reaction.Mode about in process, adding this catalyzer has become a plurality of disclosed themes.And the reaction of representing through following formula prepares a large amount of dichlorosilane needs catalyzer:
2HCl+Si→H 2SiCl 2 (3)
Wagner (US 2499009) has used a large amount of copper halides in the segmentation calcination method, be used to the copper-silicon materials that promote that dichlorosilane forms with preparation.Yet the copper of required batch processing, high temperature annealing and high density makes this method become infeasible, and comprises that for processing the refuse of a large amount of copper has caused severe environmental problem.Downing (US 4314908) has instructed so a kind of method, that is, at high temperature, cupric oxide and metallurgical grade silicon are calcined in hydrogen atmosphere, on the surface of silicon, to produce the copper that distributes very evenly.Mui (US 5250716) discloses through making cuprous chloride vapor and pasc reaction form copper-silicon alloy.Wakamatsu (DE19654154) instruction uses the copper silicide catalyzer can prepare Trichloromonosilane.People such as Margaria (US 6057469) have described the copper that deposits on the silicon particle surface.People such as Bulan (U.S. Patent application 2004/0022713A1) point out that copper must add with the particulate forms thinner 30～100 times than silicon particle, will be effective.Selectively, in metallurgical process,, can copper be added in described (bulk) in bulk silicon through copper being added in the silicon with the form of metal element copper or the form of copper compound.Yet in order to play same catalytic effect, this interpolation in bulk must be to be higher than the concentration when only being added to copper on the said silicon face far away.The copper of the greater concn that interpolation in bulk is required has produced challenge to the useless silicon that effective processing comprises unnecessary copper.
In all previous like this methods, considerable work proposes the copper of the very fine unpack format of preparation, uses the method for strict control that the copper of these meticulous forms closely and is effectively mixed with silicon matter then.In the district outside hydrogenation reaction zone said copper coating is handled; For example, Downing (US 4314908) has also proposed the problem of additional processing; Material in order to prevent to handle forms oxide coatings once more, can suppress said hydrogenation subsequently and form oxide coatings.These special methods always can increase the cost of whole process of preparation, and can make the preparation process complicated.
When the time spent of doing of considering said promotor or catalyzer, all existing methods all can't be explained the influence of natural oxide on surface on silicon.Native oxide on the silicon metal can hinder copper to combine with the effective of said silicon face; And then can reduce effective interpolation of said catalyzer; The beneficial effect that perhaps postpones said catalyzer is up in said process, removing said native oxide through other chemical action.Said native oxide can be removed through violent grinding to a certain extent.But in case said oxide compound is removed, said silicon just must be placed under the condition of anaerobic, and this is very difficult with expensive method in practical commercial is produced.
Therefore, advantageously have a kind of simple method and be used for forming active catalyst species, thus the yield of raising hydrogen-oxygen silane.Utilize effective and active catalyzer, can prepare hydrogen-oxygen silane from the reaction in silicon and hydrogen and chlorine source.Said chlorine source can be hydrogenchloride, silicon tetrachloride or the combination of the two.And according to purpose, when using said effective catalyst, the ratio through regulating hydrogen and chlorine, the residence time of gas and temperature of reaction and pressure change the ratio of dichlorosilane and Trichloromonosilane.
Summary of the invention
In order to use silicon to generate effective catalyzer, the difficulty of being brought by the native oxide on the silicon face can overcome through the reaction of using following type, wherein, at first said silicon is exposed in the reducing atmosphere, to remove said oxide on surface.Hydrogen at high temperature can be realized this point through following reaction:
H 2+ SiO 2(solid-state) → Si (metal)+H 2O (steam) (4)
If the silicon of gained is remained in the environment of anaerobic, the surface of gained silicon is substantially free of oxide compound so.
Cuprous chloride is reducible material, and it at high temperature can be rapidly by hydrogen reduction:
CuCl+H 2→ 2HCl+Cu (metal) (5)
In hydrogen atmosphere, when temperature was higher than about 275 ℃, said reduction reaction (5) can take place automatically.
Through reaction (1) perhaps in the process of (2) preparation Trichloromonosilane, with commercially available metallurgical grade silicon or refining level silicon as raw material.These silicon itself have native oxide and are present on the said silicon face.In the business practice of routine, said silicon is ground and is screened, so that the granularity of the real needs that satisfy selected process design to be provided.About 200 microns granularity is suitable in many technologies; But granularity is not any difficult problem; As long as particle is enough little, thereby can for example in fluidized-bed reactor or stirred bed reactor, operate, wherein be easy to make gas to contact with said silicon particle at hybird environment.
Through the copper of (alloying) significant quantity of on the silicon face of said oxide-free, mixing, utilizing of said copper is very good, and it is very low to reach the required copper amount of said beneficial effect.When under normal temperature and condition of normal pressure, carrying out the preparation of silicon hydride chlorid,, can obtain this beneficial effect through copper and the silicon of supplying additional content according to demand.
Usually; In order to prepare silicon hydride chlorid according to reaction (1,2 or 3); Silicon is added in container such as fluidized-bed reactor or the mechanical agitation bed bioreactor, and said reactor drum is between 275 ℃～550 ℃ of the normal operating conditions, and have the charging in gaseous hydrogen and chlorine source.Said chlorine source can be hydrogenchloride, silicon tetrachloride or their both combinations.When not having hydrogenchloride, taken place not by catalytic reaction:
SiCl 4+H 2→HCl+HSiCl 3(6)
Do not have silicon to generate, but formed a spot of HCl (＜1%).Can regulate temperature, reactor residence time and hydrogen and muriatic concentration, with the product mixture of preparation needs.Be higher than under any temperature of 275 ℃, hydrogenchloride can produce serious erosion to said silicon through reaction (2).The combination of reaction (2) and reaction (6) can obtain reaction (1).The effect of said silicon is from reaction environment, to remove HCl, and the equilibrium concentration that will react (1) moves right, thereby increases the total recovery of silicon hydride chlorid.
Simultaneously, the surface of said silicon can be corroded by said hydrogen, to remove the moisture of oxide on surface and absorption:
H 2+SiO(H)→Si+H 2O (7)
Reaction (6) and (7) is at H 2Carry out under the excessive situation.Simultaneously, reaction (6) and (7) combination is removed any oxide compound or moisture with at least a portion surface from said silicon.Then, the silicon face that is substantially free of oxide compound of gained can be accepted active copper metal effectively, and combines with it.
Then, with the form of cuprous chloride (CuCl) copper is added in the reactor drum most effectively, under 275 ℃～550 ℃, the reduction reaction of carrying out with excess hydrogen has taken place, formed copper metal and other HCl according to reaction formula (5).At least a portion that deposits to said silicon at the copper for preparing on the atomic basis through chemical vapor deposition method is substantially free of on the surface of oxide compound, thereby forms copper-silicon alloy.Particularly, in the place very approaching with the silicon of said oxide-free, the CuCl particle can be by in-situ reducing, thereby has formed effective alloy catalyst.Said copper deposit can be made up of the copper " island " of random arrangement on said silicon face.For reaction (1), (2) and (3), said copper silicon face alloy is very effective catalyzer.Be less than at 1.0% o'clock at copper content, obtain very effective result.When the amount of copper be said copper doped silicon quality 0.01%～0.5% the time, reach especially effectively operation.Consider for environmental influence, be used to realize that the copper of required silicon hydride chlorid yield is few more, just good more, and confirm here low-level than the low one magnitude of the level that needed in the past.
Except that chlorination is cuprous, perhaps, also can use other reducible copper compound as the surrogate of cuprous chloride.Can use the mixture of cupric oxide or cupric oxide and copper metal.But, when using these materials, the unnecessary moisture that forms owing to the hydrogen reduction reaction of cupric oxide; Can cause the loss of chlorosilane; And this loss is because chlorosilane is hydrolyzed into siloxanes, and causes high-boiling-point impurity, and high boiling material impurity produces a difficult problem in processing.Another kind of suitable reducible material is a Platinic chloride.When silicon tetrachloride during, should be chosen in silicon tetrachloride and hydrogen and have the promoter metals that can promote hydrochlorination down as the chlorine source.When said chlorine source was hydrogenchloride, said promoter metals should be the metal that in the presence of silicon tetrachloride and hydrogen, can promote the hydrochlorination of silicon.
If a kind of material such as promoter metals are not associated with silicon face, it is invalid in catalyzed reaction (1) so.For example, if promoter metals is present on other inactive surface such as silicon-dioxide or the carbon, just do not find facilitation effect.Said promoter metals must be present in the surface of said silicon.On oxygen-free silicon face with in the tight adjacent areas in said promoter metals position the quick consumption of silicon takes place only.
Need promoter metals-silicon alloy be evenly distributed on the surface of silicon.It only need exist with enough amounts.And the removal of native oxide also needs not be fully or is uniform on silicon, as long as it is just passable to be enough to hold the amount of treating sedimentary promoter metals.
Keep hot conditions, to realize the preparation of one or more required silicon hydride chlorid.In order to help to prepare Trichloromonosilane according to reaction (1) from silicon tetrachloride, the temperature in the reactor drum preferably maintains 400 ℃～500 ℃.In order to help to prepare Trichloromonosilane and dichlorosilane according to reaction (2) and (3) from HCl, the temperature in the reactor drum preferably maintains 275 ℃～350 ℃.
The type of reactor drum should be convenient to mix the silicon and the reducible material that comprises promoter metals of deoxidation, thus with the reducible substance transfer of decomposability to the surface of said silicon, and said promoter metals will deposit on this surface.Particularly suitable reactor drum comprises: fluidized-bed reactor, and wherein motion gas provides mixing force; Mechanical stirring reactor, for example rotary kiln and stirred bed reactor; And tower reactor, wherein said silicon and cupric chloride particle can be with respect to descending to the hydrogen-rich gas stream that rises under action of gravity.Said hydrogenation also can carry out in dilute phase (with respect to the solids seldom of reactor volume).
In the actually operating of this process because according to reaction formula (1), (2) perhaps (3) silicon be consumed, and silicon hydride chlorid is removed from reactor drum, so need fresh silicon be added in the hydrochlorination device, to keep substantially invariable storage.Can granulous silicon be supplied with or intermittent entry with little increment continuously.When the cuprous chloride powder is supplied with granular silicon, can use single simplified system.Therefore, preferably said cuprous chloride is directly added in the reaction zone, the copper that cuprous chloride resolves in said reaction zone, and deposit to the having basically no on the oxide surface of the silicon that is present in the reaction zone.The fresh silicon of supplying with cuprous chloride has one section of short duration conditioning time in reaction zone, be used to remove its native oxide, thereby the cuprous chloride that is ready to add with next time reacts.By this method, those skilled in the art come preconditioned silicon or copper bearing material without any need for special operation, and under normal temperature and normal pressure, and general effect is a high speed production silicon hydride chlorid advantageously.
Can add other in a similar fashion can be used for promoting hydrochlorination or high pro rata yield to form the material of hydrogenant silicon hydride chlorid more.When selecting the form of promoter material, by hydrogen reduction those forms, can obtain best result under the high temperature that perhaps in reaction zone, exists of can under reaction conditions, vaporizing with the aggradation accelerant metal.This type material comprises the muriate of oxide compound, carbonate, zinc and tin and the muriate and the carbonate of ruthenium, rhenium, platinum, silver, osmium and nickel.
The realization of present method is described with indefiniteness embodiment below.
Embodiment 1
Use be ground to mean particle size be 200 microns 13, pack into the fluidized-bed reactor of diameter 122cm of the metallurgical grade silicon of 000Kg.Under the pressure of 500 ℃ temperature and 3MPa, use flow velocity to be 3350m 3The hydrogen of/hr starts reactor drum.After reactor drum reached service temperature, under the pressure of 500 ℃ temperature and 3MPa, beginning flow velocity was 3350m 3The silicon tetrachloride vapor of/hr.Obtain on not hydrogenous basis, comprising the reactor product of 20mol% Trichloromonosilane.When reactor level reduced 150Kg, this minimizing was that this process continues a couple of days by this way because reaction (1) consume silicon has begun the cycle interpolation of metallurgical grade silicon.Operate after three days, 72% equivalent of the original interpolation quality of silicon is consumed, and is replaced by the fresh metallurgical grade silicon of equivalent.On this aspect, through the mixture of preparation metallurgical grade silicon and cuprous chloride in the large vol bag (bulk bag) that 4.5 kilograms cuprous chloride is added to contain 1363 kilograms of silicon.Use pneumatic conveyor that copper/silicon mixture is transported in the lock hopper on the said fluidized-bed reactor top, the standard metallurgical grade silicon that said copper/silicon mixture is fed into said reactor drum substitutes.Soon, the consumption of hydrogen will raise significantly after adding said cuprous chloride/silicon mix.Under the condition of hydrogen not, reactor product increases to the 25mol% Trichloromonosilane.As long as cuprous chloride/silicon mix is continued to add the silicon that comes supplement consumed to fall, the yield of Trichloromonosilane will remain on the higher level.When stopping to add cuprous chloride, the output of Trichloromonosilane begins to descend, and finally returns to cuprous chloride and begins to add initial level before.The speed that descends shows that copper associates with silicon, make have only when associating silicon particle by chemical erosion to size when holding back size (～15 microns), just can be by elutriation from said reactor drum.After the conversion of Trichloromonosilane had returned to its pre-catalyst level, said reaction mass analysis revealed copper is accumulation not, yet copper is directly proportional with the amount that Trichloromonosilane reduces in the density loss from the meticulous silicon of reactor drum elutriation.
This embodiment shows the reducible material that contains promoter metals is directly added in the reaction zone that the silicon of oxide-free existed, and can cause higher Trichloromonosilane transformation efficiency.Show that also cupric chloride closely associates with silicon, and the yield of Trichloromonosilane is directly relevant with the concentration of copper in reaction mass.
Embodiment 2
The metallurgical grade silicon (mean particle size is 200 microns) that at first 50 grams is ground is put into the testing tube that diameter is 25mm, this testing tube is placed in the small-sized baking oven, and is heated to 525 ℃ temperature with mobile hydrogen.Again silicon tetrachloride being placed on temperature is in 25 ℃ the temperature bath.Through said pond supply bubble hydrogen, so that said hydrogen is saturated with silicon tetrachloride, then that these are saturated hydrogen is mobile with other hydrogen, makes H 2: SiCl 4Mol ratio be 2.0, get into the testing tube bottom contain silicon.The total flow rate of hydrogen is 12cc/min.Partition is installed in outlet at reactor tube, makes a spot of gaseous sample to be collected, and is used for gas chromatographic analysis.When the temperature in the reactor drum was 525 ℃, the yield of Trichloromonosilane was 4.6%.
Embodiment 3
Use with embodiment 2 in identical equipment, restrain metallurgical grade silicons with 49 and be put in the said reactor tube, and in hydrogen atmosphere, be heated 525 ℃.After silicon is exposed to hot hydrogen, 0.39 gram cuprous chloride is added in the said reactor drum, make said hydrogen continuous flow simultaneously.Let hydrogen stream cross the temperature bath of silicon tetrachloride then, said elute is taken a sample.Under the condition of hydrogen not, the concentration of Trichloromonosilane is 6.14%.
Embodiment 4
Use with embodiment 2 in identical equipment, restrain silicon with 50 and pack in the reactor drum, on said silicon, deposited 1% platinum in advance.When the normal stream of hydrogen and silicon tetrachloride at 525 ℃ down during reaction, under the condition of hydrogen not, the concentration of Trichloromonosilane is 6.05%.
Embodiment 5
Use with embodiment 2 in identical equipment, 49.9 gram metallurgical grade silicons and 0.1 are restrained on glue silicon the mixture of the 5% platinum reactor drum of packing into.Under the condition of hydrogen not, the concentration of Trichloromonosilane is 4.28%.
Embodiment 6
Use with embodiment 2 in identical equipment, 49 gram white quartzs and 0.1 are restrained on gac the mixture of the 5% platinum reactor drum of packing into.With embodiment 2 under the identical standard conditions, the concentration of the Trichloromonosilane in the elute is＜0.1%.
In these exemplary embodiments, show that reaction system must have active promoter metal and Pure Silicon Metal source simultaneously in order to promote hydrogenation.Do not have promoter metals can cause the yield (embodiment 2) that reduces, and do not having under the situation of silicon,, still can not transform (embodiment 6) even have active hydrogenation catalyst.In order to access better transformation efficiency, active promoter metal must closely associate with silicon (embodiment 2 and 4 and embodiment 5 compare).
Embodiment 7
Use with embodiment 2 in identical equipment, restrain metallurgical grade silicons with 50 and pack in the reactor drum, and under the hydrogen chloride flow of the hydrogen stream of 12cc/min and 6cc/min, be heated to 300 ℃.After silicon is exposed to hot hydrogen and hydrogen chloride mixture for several hour, in reactor drum, add 0.4 gram cuprous chloride, hydrogen/hydrogen chloride flow continues simultaneously.When according to the said sampling among the embodiment 2, comprise the dichlorosilane of Trichloromonosilane and several percentage points in the elute.Do not having under the situation of copper-silicon alloy catalyst the dichlorosilane of trace is only arranged.
In this manual, with reference to some embodiment preferred the method that preparation contains silicon hydride chlorid is described.For a person skilled in the art, other embodiment can become obvious through considering this specification sheets or hands-on approach disclosed herein.This specification sheets and embodiment only are as a kind of example, and the scope and the flesh and blood of the real protection of the present invention are provided by appending claims.

Claims (21)

1. method that is used to prepare one or more silicon hydride chlorid comprises:
In reducing atmosphere, have the silicon particle of oxide on surface through heating, remove deoxidation from least a portion surface of said silicon particle, have the silicon particle in the zone of at least one oxide-free with preparation;
The metal deposition of hydrochlorination that can promote silicon with chemical vapor deposition method is to the zone of said oxide-free, and with preparation promoter metals-silicon face alloy, described chemical vapor deposition method comprises that reduction contains the reducible material of said metal; And
The silicon of hydrogen, chlorine source and doping promoter metals is reacted, to prepare one or more silicon hydride chlorid.
2. method according to claim 1, wherein said to remove, deposit and react be under 275 ℃～550 ℃ temperature, to carry out.
3. the method for preparing silicon hydride chlorid according to claim 1, said silicon hydride chlorid comprises Trichloromonosilane and dichlorosilane, wherein:
Said chlorine source is a silicon tetrachloride; And
Said promoter metals is the metal that in the presence of silicon tetrachloride and hydrogen, can promote the hydrochlorination of silicon.
4. method according to claim 3, wherein said to remove, deposit and react be under 400 ℃～500 ℃ temperature, to carry out.
5. the method for preparing silicon hydride chlorid according to claim 1, wherein said silicon hydride chlorid comprises Trichloromonosilane and dichlorosilane, wherein:
Said chlorine source is a hydrogenchloride; And
Said promoter metals is the metal that in the presence of hydrogen, can promote the hydrochlorination of silicon.
6. method according to claim 5, wherein said to remove, deposit and react be under 275 ℃～350 ℃ temperature, to carry out.
7. method that is used to prepare one or more silicon hydride chlorid comprises:
Hydrogen, chlorine source and silicon with oxide on surface are merged;
Said hydrogen, chlorine source and silicon are heated to sufficiently high temperature, thereby oxygen is removed from least one zone of silicon face;
The silicon that will have the oxide-free zone contacts with reducible material, and said reducible material comprises the metal of the hydrochlorination that can promote said silicon;
Said reducible material is heated to enough temperature, makes this material be reduced, and with the zone of said metal deposition to said oxide-free, with preparation promoter metals-silicon face alloy; And
The silicon of said hydrogen, chlorine source and doping promoter metals is reacted, to prepare one or more silicon hydride chlorid.
8. method according to claim 7, wherein said Heating temperature will reach 275 ℃～550 ℃, and described reaction is under 275 ℃～550 ℃ temperature, to carry out.
9. the method for preparing silicon hydride chlorid according to claim 7, said silicon hydride chlorid comprises Trichloromonosilane and dichlorosilane, wherein:
Said chlorine source is a silicon tetrachloride; And
Said promoter metals is the metal that in the presence of silicon tetrachloride and hydrogen, can promote the hydrochlorination of silicon.
10. method according to claim 9, wherein said Heating temperature will reach 400 ℃～500 ℃, and described reaction is under 400 ℃～500 ℃ temperature, to carry out.
11. the method for preparing silicon hydride chlorid according to claim 7, said silicon hydride chlorid comprises Trichloromonosilane and dichlorosilane, wherein:
Said chlorine source is a hydrogenchloride; And
Said promoter metals is the metal that in the presence of hydrogen, can promote the hydrochlorination of silicon.
12. method according to claim 11, wherein said Heating temperature will reach 275 ℃～350 ℃, described reaction is under 275 ℃～350 ℃ temperature, to carry out.
13. according to claim 1 or 7 described methods, wherein said promoter metals be less than said doping promoter metals silicon quality 0.1%.
14. according to claim 1 or 7 described methods, wherein said promoter metals is a copper, and copper be less than said doping promoter metals silicon quality 1.0%.
15. according to claim 1 or 7 described methods, wherein said promoter metals be said doping promoter metals silicon quality 0.01%～0.5%.
16. according to claim 1 or 7 described methods, wherein said reducible material is a cuprous chloride.
17. according to claim 1 or 7 described methods, wherein said reducible material is a cupric oxide.
18. according to claim 1 or 7 described methods, wherein said reducible material is a Platinic chloride.
19. a method that is used to prepare one or more silicon hydride chlorid comprises:
In container, the mixture that comprises hydrogen, chlorine source and have the silicon of oxide on surface is heated the sufficiently long time under a temperature, thereby oxygen is removed from least a portion surface of said silicon;
In said container; Under reducing atmosphere; The said silicon on part oxide-free surface contacts under sufficiently high temperature the reducible material that makes the metal that comprises the hydrochlorination that can promote silicon with having at least; Make that this reducible material is reduced, and make said metal deposition to the surface of the oxide-free of said silicon, with preparation promoter metals-silicon face alloy; With
The silicon of said hydrogen, chlorine source and doping promoter metals is reacted, to prepare one or more silicon hydride chlorid in said container.
20. method that is used to form the reaction mass that contains promoter metals; This method comprises: with silicon particle, hydrogen, chlorine source with comprise in the container of reducible material under 275 ℃～550 ℃ of the metal that can promote hydrochlorination and keeping the sufficiently long time; Make oxygen be removed from the surface of said silicon particle; Said reducible material is reduced, and through chemical vapor deposition method with said metal deposition to the surface of said silicon particle, to form promoter metals-silicon face alloy.
21. method according to claim 20, wherein:
Described reducible material is a cuprous chloride; And
Described metal is a copper, and it is deposited to through chemical vapor deposition method at least a portion surface of said silicon, to form copper-silicon face alloy.
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