Classifications

• • 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
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • 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
  • B01J23/74—Iron group metals
  • B01J23/755—Nickel
• • 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
  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/24—Chromium, molybdenum or tungsten
  • B01J23/26—Chromium
• • 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
• • 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
  • B01J23/74—Iron group metals
  • B01J23/75—Cobalt
• • 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
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
• • 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
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/86—Chromium
• • 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
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/86—Chromium
  • B01J23/868—Chromium copper and chromium
• • 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
  • C01B33/04—Hydrides of silicon
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
  • H01L21/02518—Deposited layers
  • H01L21/02521—Materials
  • H01L21/02524—Group 14 semiconducting materials
  • H01L21/02532—Silicon, silicon germanium, germanium
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
  • H01L21/02612—Formation types
  • H01L21/02617—Deposition types
  • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD

Definitions

• the invention relates to a process for the preparation of higher hydridosilanes by means of a dehydropolymerization reaction of lower hydridosilanes, to the higher hydridosilanes prepared by the process, and to the use of the higher hydridosilanes for producing electronic or optoelectronic component layers and for
• Hydridosilanes or their mixtures in particular higher hydridosilanes or their mixtures, are described in the literature as possible starting materials for the production of silicon layers. Hydridosilanes are compounds which essentially contain only silicon and hydrogen atoms. Hydridosilanes according to the present invention are gaseous, liquid or solid and - in the case of solids - substantially soluble in solvents such as toluene or cyclohexane or in liquid silanes such as cydopentasilane. Examples which may be mentioned are monosilane, disilane, trisilane and cydopentasilane.
• EP 1 087 428 A1 Process for the preparation of silicon films in which hydridosilanes having at least three silicon atoms are used.
• EP 1 284 306 A2 describes inter alia. Mixtures comprising a hydridosilane compound having at least three silicon atoms and at least one hydridosilane compound selected from cydopentasilane, cyclohexasilane and silylcyclopentasilane, which can also be used for the production of silicon films.
• Higher hydridosilanes can be prepared, for example, by dehalogenation and polycondensation of halosilanes with alkali metals (GB 2 077 710 A).
• a disadvantage of this method is that partially halogenated silanes as impurities incurred in particular for the further processing of the product for the
• transition metal complexes homogeneous catalysis, US 5,700,400 A for Group 3B-7B complexes, and 8-ie the transition metals / lanthanides without Cu and Zn groups, JP 02-184513 A) or e
• determ mten on a support immobilized transition metals heterogeneous catalysis; US Pat. No. 5,700,400 A for ruthenium, rhodium, palladium or platinum immobilized on carbon, S1O2 or Al2O3
• transition metal complexes heterogeneous catalysis, US Pat. No.
• the process according to the invention is particularly well suited for the preparation of higher hydridosilanes or their mixtures consisting of or substantially comprising higher hydridosilanes with 2 ⁇ n ⁇ 20.
• higher hydridosilanes or their mixtures consisting of or substantially comprising higher hydridosilanes with 2 ⁇ n ⁇ 20.
• Hydridosilanes that meet substantially the above formulas with 2 ⁇ n ⁇ 10.
• Such a mixture usually contains Si 2 H 6 , S 13 H 8, n-Si 4 Hi 0 , n-Si 5 Hi 2 , n-Si6Hi 4 as main components, in addition to optionally n-Si 7 Hi 6 , n-SisHis, n- SigH 2 o and n-SiioH 22 as minor components.
• Means and ways in which the number average molecular weight of the product is determined and the method according to the invention can be stopped when a corresponding number average molecular weight is reached are known to the person skilled in the art.
• the process according to the invention is particularly well suited for the preparation of linear hydridosilanes.
• Other products typically produced in lower yield may be branched hydridosilanes such as i-Si6Hi and cyclic hydridosilanes such as cyclopentahydridosilane (cycloS15H10).
• cycloS15H10 cyclopentahydridosilane
• bi- or polycyclic hydridosilanes can also be formed.
• the proportion of these secondary components is in total typically at most 10% by weight, in each case based on the sum of the hydridosilanes and the secondary components.
• a heterogeneous catalyst is to be understood as meaning a catalyst which is present in a different phase than the reactants.
• the catalyst used in the process according to the invention which comprises metal or metal oxide supported on a carrier, is to be understood as meaning a catalyst which mixes up or blends with an inert inert substance (the "carrier") for this chemical reaction per se and less (as compared to the catalyst material) substantially heterogeneous catalyst material applied to the surface of the carrier material by coating, precipitation, impregnation or mixing elementary or in connection with the carrier and / or under atomic
• the heterogeneous catalyst material employed in the process of the invention comprises copper, nickel, chromium and / or cobalt, which is 1) supported on the respective support, i. as an elemental metal on the support and / or with atomic involvement in the crystal or layer structure of the support material, and / or 2) oxide supported on the support, i. a) as a metal oxide of a defined oxidation state, b) as a mixed-valent compound of various valent oxides or c) at least one oxide in combination with the elemental metal, each as a chemical compound (s) on the support and / or incorporated into the Crystal or
• Layer structure of the carrier material may be present or may.
• Preferred lower hydridosilanes which offer the advantage of being readily available are the compounds monosilane, disilane and trisilane. Because of your
• monosilane and disilane are particularly preferred.
• Very particularly preferred is a mixture of monosilane and disilane, which leads to particularly good yields.
• Preferred carriers are large-area substances, in particular activated carbon,
• Alumina in particular alumina
• silica silica gel
• silicates kieselguhr
• talc silicates
• kaolin clay
• titanium dioxide zirconium oxide
• zeolites since these are also known as
• the at least one heterogeneous catalyst in particular the heterogeneous catalyst material which is applied to the support, preferably comprises
• a preferably usable catalyst can be prepared by 1) impregnating the
• Catalysts comprising Cu, Ni, Cr or Co supported on a support can be prepared particularly well under the choice of reducing conditions, whereas catalysts comprising supported Cu, Ni, Cr or Co can be prepared particularly well under the choice of oxidizing conditions.
• the metal salt compounds, in particular nitrates can continue to be first converted into the oxidic form.
• the drying takes place at temperatures of 80 to 150 ° C.
• Calcination is preferably carried out at temperatures of 300-600 ° C.
• the reduction is preferably carried out at temperatures of 150 ° C - 500 ° C.
• the percentage by weight of the supported Cu, Ni, Cr or Co or the oxide of Cu, Ni, Cr or Co is preferably between 0.5 and 65 wt .-% based on the total mass of the catalyst (support + catalyst material ). This weight percentage can be achieved by applying known concentrated solutions to a calcined carrier and weighing after drying and second
• Calcination (optionally under reducing or oxidizing conditions and assuming that no metal is lost) are determined.
• the proportion of the catalyst is preferably 0.001-0.5, particularly preferably 0.01-0.1, very particularly preferably 0.02-0.06% by weight, based on the Mass of the liquid phase.
• the GHSV gas hourly space velocity
• gas volume flowed through at STP conditions per h / catalyst volume preferably 0.1-4000 h -1 , particularly preferably 1 - 3000 h -1 , very particularly preferably 10-1000 h -1 .
• the temperature at which the process according to the invention is carried out is not critical.
• the process according to the invention for the preparation of higher hydridosilanes is preferably carried out at temperatures of 0-400.degree. It is preferably carried out at temperatures of 35-170 ° C., very particularly preferably at temperatures of 140-160 ° C.
• absolute pressures of 1 to 200 bar are preferably used. Below 1 bar, the sales are often unsatisfactory, and above 200 bar absolutely the material requirements do not justify the effort.
• the reaction time can be a few hours to several days.
• the proportion of higher silanes increases with the reaction time.
• the process according to the invention can furthermore be carried out in the presence or absence of a solvent. Preferably, however, it is carried out in the presence of a solvent.
• a solvent In principle, all solvents which react neither with the starting materials nor with the products are suitable.
• Preferably used are linear, branched and cyclic aliphatic and substituted or unsubstituted
• aromatic hydrocarbons especially cyclic alkanes, benzene and toluene
• Ethers especially dialkyl ethers, furans or dioxanes
• dimethylformanide ethyl acetate or butyl acetate.
• the process according to the invention can be carried out in the presence or absence of gases which support the course of the reaction.
• gases e.g. even non-reactive gases, in particular nitrogen, argon or helium, for diluting the
• Reaction mixture can be used. Furthermore, in support of the
• the proportion of hydrogen is initially not limited. It depends on the starting materials (lower hydridosilanes and
• Partial pressure of the hydrogen is preferably 1 to 200% of the pressure of the hydridosilanes used when gaseous silanes are used.
• the proportion of hydrogen is chosen so that the partial pressure of the hydrogen corresponds to at least 5% of the total pressure. Preferred is a range of 5% to 80%, more preferably a range of 5% to 50%.
• disadvantageous relatively high molecular weight secondary components in particular higher hydridosilanes having more than 20 Si atoms
• these can be removed by methods known to the person skilled in the art, in particular via distillation or via the use of adsorptive processes. Purification is also possible using a cross-flow membrane process with at least one membrane separation step using a permeation membrane.
• the invention also relates to the higher hydridopolysilanes or their mixtures prepared by the process according to the invention. These higher hydridopolysilanes or their mixtures prepared according to the invention are suitable for a large number of uses. They are particularly suitable for the production of electronic or optoelectronic component layers. The invention thus also relates to the use of the higher hydridosilanes obtainable by the process according to the invention for producing optoelectronic or
• the higher hydridosilanes obtainable by the process according to the invention are suitable for the production of charge transporting components in optoelectronic or electronic components.
• the higher hydridosilanes obtainable by the process according to the invention are furthermore suitable for the preparation of silicon-containing layers, preferably elemental silicon layers.
• Stainless steel reactors are preferably used, which are equipped with a glass liner, a thermocouple, a pressure transducer, a liquid sampling, an inlet and an outlet for the educts as gases or liquids, and a
• Catalyst basket are equipped. After filling the reactor basket with the reactor basket.
• the catalysts are repeatedly inertized and then with
• reaction times are of course dependent on the selected educts and
• reaction parameters from. are at
• Reaction temperatures of 40 ° C and pressures of 60 bar for about 1 - 24 hours.
• the resulting product mixture consisting of the higher hydridosilanes formed, if appropriate, solvent and possibly unreacted starting materials, can be used after removal of the catalyst basket for use in the semiconductor or photovoltaic sector since, given the purity of the starting materials, no contamination of interfering secondary components is required are expected. If, in the reaction for the further purposes, interfering relatively high molecular weight secondary components (in particular higher hydridosilanes having more than 20 Si atoms) have accumulated, they can be separated off prior to use of the reaction product by methods known to the person skilled in the art, in particular by distillation or by the use of adsorptive processes become. Purification is also possible using a cross-flow membrane process with at least one membrane separation step using a permeation membrane.
• MRS 500 Parrlnstruments is filled with the respective heterogeneous catalyst in the amount shown in Table 1 below (catalyst basket). Thereafter, the reactor is rendered inert three times (alternating argon and vacuum) and filled with 30 ml of dried toluene.
• the reactor Via the gas supply line, the reactor (internal volume 70 ml) is charged at room temperature with 60 bar SiH and heated to the particular temperature indicated. By starting the stirrer (700 rpm), the reaction is started. After a reaction time of 20 h, a liquid sampling takes place. The withdrawn liquid is analyzed by gas chromatography.
• the evaluation of the samples was carried out according to the method of the internal standard (in this case heptane).
• the stated product amount corresponds to the sum of detected silanes.
• k was determined between cyclopentasilane and heptane.

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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)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Catalysts (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2009
  • 2009-10-02 DE DE102009048087A patent/DE102009048087A1/de not_active Ceased
• 2010
  • 2010-08-13 WO PCT/EP2010/061825 patent/WO2011038977A1/de not_active Ceased
  • 2010-08-13 CN CN201080044156.XA patent/CN102639235B/zh not_active Expired - Fee Related
  • 2010-08-13 EP EP20100742002 patent/EP2482976B1/de not_active Not-in-force
  • 2010-08-13 JP JP2012531295A patent/JP2013506541A/ja active Pending
  • 2010-08-13 US US13/498,206 patent/US8709369B2/en not_active Expired - Fee Related
  • 2010-08-13 KR KR1020127008245A patent/KR20120081996A/ko not_active Withdrawn
  • 2010-09-29 TW TW099133065A patent/TWI495613B/zh not_active IP Right Cessation

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