AU2013224703A1

AU2013224703A1 - Polysilane processing and use

Info

Publication number: AU2013224703A1
Application number: AU2013224703A
Authority: AU
Inventors: Gudrun Annette Auner; Christian Bauch; Rumen Deltschew; Gerd Lippold
Original assignee: Spawnt Private SARL
Current assignee: Nagarjuna Fertilizers and Chemicals Ltd
Priority date: 2006-07-20
Filing date: 2013-09-05
Publication date: 2013-09-26
Anticipated expiration: 2027-07-20
Also published as: AU2013224703B2

Abstract

Abstract The invention relates to a method for the final product related manufacture of low-molecular, medium-molecular, and high-molecular halogenated polysilanes, the distillation thereof into selected fractions, the direct deposition of 10 silicon from the gas phase or a liquid phase of polysilane mixtures or polysilanes, the hydrogenation or derivatiza tion of halogenated polysilanes, and the processing into final products in an adequate system. (7805457_1):MRR

Description

1 F1Polysilane Processing and Use The invention is directed to a method for the final prod uct-related production of halogenated polysilanes, the dis 5 tillation, hydrogenation or derivatization thereof and the processing into final products in an adequate system. As polysilanes in the sense of the inventive method chemi cal compounds are designated which are characterized by at 10 least one direct linkage Si-Si. Polysilanes can contain linear Sin chains and/or Si, rings as well as chain branch ings. Halogenated polysilanes in the sense of the inventive meth 15 od are polysilanes the substituents of which largely con sist of halogens X = F, Cl, Br, I as well as of hydrogen. Halogenated polysilanes in the sense of the inventive meth od are poor with respect to hydrogen with a ratio H : X 1 5. 20 Preparation of the polysilanes The mixture of halogenated polysilanes which can serve, among others, for the production of silicon is produced in 25 a plasma chemical step from SiX 4 and H 2 . This method is de scribed in the patent application of Prof. Dr. Auner "Ver fahren zur Herstellung von Silizium aus Halogensilanen" with the number PCT/DE2006/00089. The plasma reaction can be carried out, for instance, through continuous stimula 30 tion (continuous wave): (7805457_1):MRR 2 A H 2 /SiX 4 vapour mixture is stimulated by means of an elec tric or electromagnetic alternating field and is converted into the plasma-like condition. Dependent on the reaction conditions liquid, semi-solid or solid mixtures of halogen 5 ated polysilanes are produced. According to the present understanding polysilanes with 2 to 6 silicon atoms are designated low-molecular pol ysilanes, polysilanes with 7 to 14 silicon atoms are desig 10 nated medium-molecular polysilanes and polysilanes with at least 15 silicon atoms are designated high-molecular pol ysilanes. The selected groups are different with respect to their possibilities of further processing by distillation, hydrogenation or derivatization. 15 According to the invention it is especially advantageous to control the reaction conditions in the plasma reactor in such a manner that not only any mixture of halogenated pol ysilanes is produced but the mixture of polysilanes which 20 is most favourable for the further processing. The specific halogenated polysilanes provided for further processing can be unambiguously determined especially by means of the molecular masses as well as additional suita 25 ble determining methods. One can produce low-molecular, me dium-molecular and high-molecular halogenated polysilanes and characterize the same wherein cyclically structured polysilanes are also important with respect to the polymer ization to obtain long-chain polysilanes. 30 (7805457_1):MRR 3 It is advantageous to provide the plasma source located in the plasma reactor in several stages and to provide all possible measures for the aimed introduction of energy into a space volume as small as possible with a reaction mixture 5 as homogeneous as possible. This enables a high flow rate of the reaction mixture with largely homogeneous reaction conditions and thus largely homogeneous reaction products either. 10 It is decisive for a reaction product which is as homogene ous as possible to form the introduction of energy into the reaction plasma which has to be produced as homogeneously as possible and to provide reaction conditions as homoge 15 nous as possible in the plasma. Here it is advantageous to provide not only one plasma stimulation but several plasma stimulations which are passed subsequently by the reaction mixture. 20 In order to obtain an energy introduction into the space volume filled by the reaction mixture which is as uniform as possible it is advantageous to pulse the plasma source in order to obtain a more uniform stimulation of the reac tion mixture. 25 The same object of a more homogeneous stimulation can be obtained by exposing the reaction mixture to an additional electron flow for achieving a more stable plasma or a bet ter plasma ignition. 30 (7805457_1):MRR 4 Additionally, the reaction mixture can be quenched by elec tromagnetic coils located at the outside of the reactor so that the reaction plasma is exposed to a compression with subsequent expansion. According to the invention it is also 5 provided that the reaction mixture passes through a resona tor chamber tuned to the wave length of the stimulation source. It is advantageous to additionally expose the plasma to ra 10 diation of visible or ultraviolet light in order to be able to selectively stimulate ions or molecules in the reaction mixture. It is decisive for a continuous operation of the system 15 that the product mixture has a liquid (viscous) consistency so that it can flow out from the reactor in order to avoid occlusions. The liquid consistency of the produced mixtures of halogen 20 ated polysilanes is obtained by operating in the reactor with SiX 4 excess and H 2 content as low as possible and by holding the temperature of the reactor below room tempera ture. 25 Accordingly, it is preferably if the mol concentration of hydrogen in the used gas mixture is smaller than the mol concentration of the SiX 4 . The characterization of the prepared polysilanes is made 30 with the example of a mixture of chlorinated polysilanes as follows: (7805457_1):MRR 5 The volumetric determination of the chlorine content (chlo ride according to Mohr) of a sample solved in an aqueous lye results in the empirical formula SiCl 2 +x for the mixture 5 of polysilanes wherein x varies between 0 and 1 according to the mean chain length so that one can also speak of a polymer dichlorosilylene consisting of rings (x=0) and chains (0<x 1) wherein the chains are terminated with SiCl 3 groups. The structural formula of the rings is: 10 SiCl 2 n and that of the chains is: SinCl 2 n+ 2 . EDX measurements confirm an atom ratio in the product of about Si:Cl = 1:2. 2Si-i-NMR measurements show that, depend ent on the conditions of production, the product can be a 15 complex mixture of different chlorinated polysilanes. Pref erably, linear compounds are present as confirmed by the deficiency of signals of tertiary (Cl-Si/SiR3)3) and qua ternary (Si(SiR3) 4 ) silicon atoms. 'H-NMR measurements show that the product contains only traces of hydrogen (Si-H 20 linkages). The obtained mixtures of halogenated polysilanes are desig nated low-molecular, medium-molecular and high-molecular polysilanes. The mixture of low-molecular polysilanes con 25 sists largely of hexachlorodisilane (Si:Cl = 1:3) and octa chlorotrisilane Si 3 Cl 8 (Si:Cl = 1:2.67) . These two compo nents can be separated by distillation. Separation of the mixture of polysilanes: 30 (7805457_1):MRR 6 Individual components or fractions can be obtained from the product mixture, for example by distillation. 1. Hexachlorodisilane escapes at first at a tempera 5 ture of about 144 0 C/1013 hPa wherein it can be al ready separated in the mixture in a vapour-like condition during the polysilane synthesis and can be condensed (for instance 0 0 C). 10 2. The next fraction is formed by the lower chlorinat ed oligosilanes, as for instance the octachloro trisilane, the decachlorotrisilane and the deca chloroisotetrasilane. 15 3. The polysilanes the decomposition temperatures of which are below the boiling points at normal pres sure remain as residue. Other separation methods, as vacuum distillation, sublima 20 tion, chromatography, selective crystallisation, selective solving and centrifugation, are also suitable for separat ing the polysilanes of different molar weights from one an other. 25 Hydrogenation of the polysilanes: By the hydrogenation of the halogenated polysilanes partly hydrogenated and perhydrogenated compounds can be obtained, i.e. the halogen atoms are partly or completely replaced by 30 hydrogen atoms. The hydrogenation can be carried out in in ert solvents, as ethers, toluene etc., wherein as hydro (7805457_1):MRR 7 genation agent preferably metal hydrides and metalloid hy drides are suited. Sodium aluminum hydride and several bo ron hydrides, as for instance sodium boron hydride, are to be especially mentioned in this connection. During the hy 5 drogenation one should operate at temperatures (RT or low er) as low as possible in order to suppress a decomposition of the formed polysilanes. Preferably, only the desired fractions are hydrogenated so that a product/product mix ture as uniform as possible is obtained. 10 Potential uses of the prepared polysilanes: 1. The complete pyrolysis of the product mixture or of individual components (halogenated polysilanes) re 15 sults in the formation of silicon which, for in stance, can be used for photovoltaic or microelec tronic purposes if correspondingly pure starting compounds are used for the production of the pol ysilane. 20 2. After the distillative separation of the product mixture the components with high vapour pressure can be used for the separation of silicon layers (for instance a-Si, monocrystalline or polycrystal 25 line silicon) from the gaseous phase on heated sub strates wherein a heat treatment can be carried out inductively or by infrared radiation depending on the carrier material. 30 3. For this, for instance, the hexachlorodisilane and the lower oligosilanes are suited wherein silicon (7805457_1):MRR 8 layers can be already deposited from temperatures of 400-500 0 C not only in the presence of H 2 but also without H 2 . For this, the substances are passed in a vapour-like condition, also in a mix 5 ture with a carrier gas (for instance H 2 ), over the heated substrate. 4. The components with low vapour pressure can be also used for the layer deposition of silicon from the 10 product mixture or after separation of the frac tions with higher vapour pressure if they are ap plied to a heatable substrate in substance or as solution and are pyrolyzed. 15 5. The deposition of silicon on the surfaces of sub strates or the heat aftertreatment of a silicon layer produced on a substrate can be used for the formation of a compound with the substrate. So, for instance, the surface of metal substrates can be 20 modified by the production of a metal silicide lay er in order to obtain an increased abrasion re sistance, a higher hardness or another surface treatment. 25 6. By the hydrogenation of the product mixture or of individual components completely or partly hydro genated polysilanes can be obtained which are espe cially suited for the deposition of silicon layers or substrates at low temperature, for instance 30 (SiH 2 )n - n Si + n H 2 . Hereby, the volatile hydro genated oligosilanes can be used for depositions (7805457_1):MRR 9 from the gaseous phase. Then the less volatile hy drogenated polysilanes can be applied onto a carri er in an undiluted manner or as solution in inert solvents (for instance toluene) and can be decom 5 posed by suitable measures (for instance heating, ultraviolet light etc.) so that a silicon layer is formed. 7. By the derivatization of the product mixture or of 10 individual components organopolysilanes can be ob tained, as for instance partly methylated or per methylated compounds of the general formula SinXaMeb (a + b = 2n) and SifXcMed (c + d = 2n +2) . Then the organopolysilanes can be introduced into polymers, 15 for instance by suitable coupling reactions (for instance Wurtz-couplings) or can be grafted onto existing polymers in order to use the special opti cal or electronical characteristics of the pol ysilane chain. In the inorganic synthetic chemistry 20 different methods for the chemical conversion of differently substituted polysilanes by chain split ting or ring opening as well as the partial re placement of substituents by, for instance, halo gens are known. These methods can be applied to the 25 primary polysilane mixture, to individual fractions after a separation, to separated pure compounds or to daughter products of the partly or complete sub stitution of the halogen atoms in the corresponding polysilanes. So, for instance, completely organo 30 substituted cyclic silanes can be converted by ring opening into chains which have halogen substituents (7805457_1):MRR 10 only at the ends or at completely organosubstituted cyclosilanes only one or two substituents can be replaced by halogens under adapted conditions so that the ring system is maintained. A direct use of 5 suitably derivatisized polysilanes, for instance in the form of thin layers on suitable substrates, is possible. The manufacture of LED's is a possible use of the organopolysilanes. 10 8. Polysilanes having individual or several hydrogen substituents can be added to C-C multiple bonds by hydrosilylation so that, dependent on the reaction partners and the reaction conditions, hydrogen can be replaced by organosubstituents or copolymers 15 with organic compounds as well as polysilane side chains at organic polymers can be produced. 9. Suitable C-substituted polysilanes produce silicon carbide if they are used as precursors and suitable 20 nitrogen-substituted polysilanes produce silicon nitride when used as precursors. In this manner layers of silicon carbide or silicon nitride are accessible after an adapted processing of the pre cursors. 25 10. After separation (for instance distillatively) the halogenated polysilanes can be also used as fine chemicals for syntheses. So, for instance, hexa chlorodisilane which, dependent on the plasma pro 30 cessing, is a main component of the product mixture (7805457_1):MRR 11 can be used for deoxygenation reactions in the syn thetic chemistry. The inventive method for the use of polysilanes is shown in 5 5 drawings. Drawing 1 shows the complete method scheme for processing. Drawing 2 shows the use of the method scheme for the depo 10 sition of bulk silicon from halogenated polysilanes of small molar weight, as for instance hexachlorodisilane. Drawing 3 shows the use of the method scheme for the hydro genation and the deposition of thin layer silicon from hy 15 drogenated polysilanes of small molar weight, as for in stance disilane. Drawing 4 shows the use of the method scheme for the par tial methylation of halogenated polysilanes of medium molar 20 weight, as for instance decachlorotetrasilane, and the fur ther processing of these organochloropolysilanes by the Wurtz-coupling of these organopolysilanes to long-chain polymers when the low-molecular and high-molecular halogen ated polysilanes are reconducted from the distillation into 25 the store tank for low-molecular/high-molecular polysilanes and the high-molecular distillation residue is directed to the direct separation of silicon. Drawing 5 shows the use of the method for the separation of 30 high-molecular halogenated polysilanes, their methylation and subsequent processing to obtain organopolysilanes when (7805457_1):MRR 12 the low-molecular and medium-molecular distillates are re conducted into the respective store tanks. List of reference numbers 5 1. Plasma reactor 2. electromagnetic radio frequency generator I 3. electromagnetic radio frequency generator II 4. electromagnetic radio frequency generator III 5. removal of predominantly low-molecular halogenated 10 polysilanes 6. removal of predominantly medium-molecular halogen ated polysilanes 7. removal of predominantly high-molecular halogenated polysilanes 15 8. distillation of predominantly low-molecular halo genated polysilanes 9. distillation of predominantly medium-molecular hal ogenated polysilanes 10. distillation of predominantly high-molecular halo 20 genated polysilanes 11. removal of undistilled low-molecular halogenated polysilanes 12. removal of distillation residues 13. removal of distillation residues 25 14. removal of distillation residues 15. removal of low-molecular distillates 16. removal of undistilled medium-molecular halogenated polysilanes 17. removal of distillation residues 30 18. removal of distillation residues 19. removal of distillation residues (7805457_1):MRR 13 20. removal of distillation residues 21. removal of distillation residues 22. removal of medium-molecular distillates 23. removal of undistilled high-molecular halogenated 5 polysilanes 24. removal of distillation residues 25. removal of distillation residues 26. removal of distillation residues 27. removal of distillation residues 10 28. removal of distillation residues 29. removal of high-molecular distillates 30. store tank of low-molecular halogenated polysilanes 31. store tank of medium-molecular halogenated pol ysilanes 15 32. store tank of high-molecular halogenated pol ysilanes 33. store tank of predominantly low-molecular halogen ated polysilane mixtures 34. deposition device for silicon from low-molecular 20 polysilane mixtures 35. deposition device for silicon layers from gaseous low-molecular hydrogenated polysilanes 36. hydrogenation reactor 37. store tank of liquid low-molecular hydrogenated 25 polysilanes 38. methylation reactor 39. store tank of low-molecular organopolysilanes 40. store tank of predominantly medium-molecular halo genated polysilane mixtures 30 41. deposition device for silicon from medium-molecular polysilane mixtures (7805457_1):MRR 14 42. hydrogenation reactor 43. deposition device for silicon layers from gaseous medium-molecular hydrogenated polysilanes 44. store tank of medium-molecular organopolysilanes 5 45. methylation reactor 46. deposition device for silicon from high-molecular polysilane mixtures 47. store tank of predominantly high-molecular halogen ated polysilane mixtures 10 48. deposition device for silicon layers from gaseous high-molecular hydrogenated polysilanes 49. hydrogenation reactor 50. store tank of liquid high-molecular hydrogenated polysilanes 15 51. store tank of gaseous high-molecular orga nopolysilanes 52. methylation reactor 53. store tank of liquid high-molecular orga nopolysilanes 20 25 30 (7805457_1):MRR

Claims

1. A method for the final product-related production and processing of mixtures of halogenated pol 5 ysilanes for the generation of silicon or silicon based products, characterized in that, dependent on the generated polysilane mixture of low, medium or high molar weight and the desired end product and/or intermediate product, 10 - this mixture of halogenated polysilanes in the gaseous or liquid phase is either directly led to the further processing or - is separated in one distillation column or a plu 15 rality of distillation columns in individual fractions and the distillates are directly pro cessed and are led to further processing steps, as for instance - a hydrogenation of the halogenated polysilanes or 20 - a methylation to obtain organopolysilanes, and - the polysilane mixture coming to the processing is controlled in its composition by the regula tion of the production process and the flow of substances. 25

2. The method for the final product-related production and processing of mixtures of halogenated pol ysilanes for the generation of silicon and/or sili con-based products according to claim 1, character 30 ized in that the mixtures of halogenated pol (7805457_1):MRR 16 ysilanes are produced chemically or plasma chemi cally.

3. The method for the final product-related production 5 and processing of mixtures of halogenated pol ysilanes according to claim 1 or 2, characterized in that for the control of the composition of the polysilane mixture one or more plasma reactors are subsequently passed by the supplied reaction mix 10 ture of halogen silane and H 2 and the mean molar weight of the mixture of polysilanes increases af ter passage of each plasma reactor.

4. The method for the final product-related production 15 and processing of plasma chemically produced mix tures of halogenated polysilanes according to one of the claims 1 to 3, characterized in that for controlling the composition of the polysilane mix ture in a plasma reactor a plurality of plasma 20 sources are provided and the same are passed by the reaction mixture and after each plasma source in the plasma reactor the mean molar weight of the polysilane mixture increases. 25

5. The method for the final product-related production and processing of plasma chemically produced mix tures of halogenated polysilanes according to one of the claims 1 to 4, characterized in that, de pendent on the number of plasma reactors or of 30 plasma sources, in a plasma reactor polysilane mix tures of predominantly low, medium and high molar (7805457_1):MRR 17 weight are obtained which are led to further pro cessing.

6. The method for the final product-related production 5 and processing of plasma chemically produced mix tures of halogenated polysilanes according to one of the claims 1 to 5, characterized in that the temperature of the plasma reactor or of individual components is maintained below ambient temperature 10 and the viscosity of the obtained polysilane mix ture is controlled by the mixing ratio between the hydrogen content and the halogen content of the gas mixture. 15

7. The method for the final product-related production and processing of plasma chemically produced mix tures of halogenated polysilanes according to one of the claims 1 to 6, characterized in that the plasma sources used in the plasma reactor are 20 pulsed.

8. The method for the final product-related production and processing of plasma chemically produced mix tures of halogenated polysilanes according to one 25 of the claims 1 to 7, characterized in that the plasma in the plasma reactor is periodically quenched by an additional electromagnetic alternat ing field or passes a resonator chamber tuned to the microwave source. 30 (7805457_1):MRR 18

9. The method for the final product-related production and processing of plasma chemically produced mix tures of halogenated polysilanes according to one of the claims 1 to 8, characterized in that plasma 5 pulsing and/or additional electrical discharge and/or plasma quenching alternate in the plasma re actor.

10. The method for the final product-related production 10 and processing of plasma chemically produced mix tures of halogenated polysilanes according to one of the claims 1 to 9, characterized in that the plasma in the plasma reactor is additionally radi ated with infrared light, visible light or ultravi 15 olet light.

11. The method for the final product-related production and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 10, 20 characterized in that the predominantly low molecular polysilane mixtures are led to a distil lation to obtain low-molecular halogenated pol ysilanes, as for instance Si 2 Cl 6 and Si 3 Cl 8 , in a pure condition. 25

12. The method for the final product-related production and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 11, characterized in that the distillation residue with 30 predominantly medium molar weight, as for instance (7805457_1):MRR 19 Si 5 X 12 or Si 5 Xio, is led to a direct further pro cessing or is led into another distillation column.

13. The method for the final product-related production 5 and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 11, characterized in that the polysilane mixtures with predominantly undecomposed distillable components of medium molar weight are led to a distillation to 10 obtain individual components in pure condition and/or fractions of defined boiling ranges.

14. The method for the final product-related production and processing of mixtures of halogenated pol 15 ysilanes according to one of the claims 1 to 10 and 13, characterized in that the distillates or dis tillation residues with predominantly low or high molar weights are led to a direct further pro cessing or are led into another distillation col 20 umn.

15. The method for the final product-related production and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 10, 25 characterized in that the predominantly high molecular polysilane mixtures are exposed to the separation method of the size-selective chromatog raphy to obtain polysilane fractions with high me dium molar weights. 30 (7805457_1):MRR 20

16. The method for the final product-related production and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 10 and 15, characterized in that the separation fraction 5 with predominantly low or medium molar weights is led to a direct further processing or into another distillation column.

17. The method for the final product-related production 10 and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 13 and 16, characterized in that the polysilanes with low, medium or high molar weight obtained after the dis tillation or other separation methods are hydrogen 15 ated and partly hydrogenated or perhydrogenated compounds are obtained.

18. The method for the final product-related production and processing of mixtures of halogenated pol 20 ysilanes according to one of the claims 1 to 17, characterized in that the hydrogenation is carried out in ethers and/or aromatic solvents.

19. The method for the final product-related production 25 and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 18, characterized in that metal hydrides and metalloid hydrides, preferably sodium aluminum hydride or so dium boron hydride, are used as hydrogenation 30 agents. (7805457_1):MRR 21

20. The method for the final product-related production and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 19, characterized in that the hydrogenation is prefera 5 bly carried out at temperatures below 20 'C.

21. The method for the final product-related production and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 15, 10 characterized in that the polysilanes with low, me dium and high molar weight obtained after the dis tillation are methylated and partly methylated or permethylated organopolysilanes of the formula SinXaMeb(a+b=2n) and SifXcMed(c+d=2n+2) are obtained. 15

22. The method for the final product-related production and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 14, characterized in that metalloid compounds and/or 20 metalorganic compounds, as for instance methyl lithium, methyl magnesium halide, dimethyl zinc, tetramethyl silane, are used as methylation agent.

23. The method for the final product-related production 25 and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 14 and 21 to 22, characterized in that the obtained orga nopolysilanes are introduced into polymers or are grafted onto the same. 30 (7805457_1):MRR 22

24. The method for the final product-related production and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 20, characterized in that mixtures of low-molecular 5 halogenated polysilanes are directed over a heated surface directly from the gaseous phase for the deposition of silicon and are pyrolytically decom posed there. 10

25. The method for the final product-related production and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 19, characterized in that liquid halogenated polysilane mixtures or their solutions are applied in suitable 15 solvents onto deposition surfaces and are decom posed there by pyrolysis wherein silicon is depos ited there.

26. The method for the final product-related production 20 and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 20, characterized in that hydrogenated polysilanes with high purity of selected molecular weights are di rected over heated surfaces in the gaseous phase 25 and silicon is deposited on these surfaces by py rolysis.

27. The method for the final product-related production and processing of mixtures of halogenated pol 30 ysilanes according to one of the claims 1 to 20, characterized in that hydrogenated polysilanes of (7805457_1):MRR 23 selected molecular weights are applied onto suita ble surfaces in the liquid phase or in solution and are decomposed by heating whereby silicon is depos ited on these surfaces. 5

28. The method for the final product-related production and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 20 and 24 to 27, characterized in that amorphous silicon 10 thin layers on any carrier surfaces are obtained as final product.

29. The method for the final product-related production and processing of mixtures of halogenated pol 15 ysilanes according to one of the claims 1 to 28, characterized in that polycrystalline silicon thin layers are obtained on any carrier surfaces.

30. The method for the final product-related production 20 and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 27, characterized in that monocrystalline silicon thin layers on any carrier surfaces are obtained. 25

31. The method for the final product-related production and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 27, characterized in that silicon is deposited as layer of any thickness from mixtures of halogenated pol 30 ysilanes above 400 'C or hydrogenated polysilanes above 200 0 C. (7805457_1):MRR 24

32. The method for the final product-related production and processing of mixtures of halogenated pol ysilanes according to one of the claims 1 to 19 and 5 23 to 26, characterized in that the deposited sili con layers are exposed to a heat aftertreatment. (7805457_1):MRR 25

33. Method for the final product-related production and processing of mixtures of halogenated polysilanes for the generation of silicon or silicon-based products, wherein the mixture of halogenated polysilanes is produced plasma-chemically from SiX 4 , wherein X is selected from the group consisting of F, Cl, Br, I, and H, and H 2 , wherein X is halogen and wherein the plasma sources to be used in the plasma reactor are pulsed and/or the plasma in the plasma reactor is periodically quenched by an additional electromagnetic field or lead through a resonator chamber which is tuned to a microwave source, wherein the produced halogenated polysilanes have a ratio of H: X < 1:5.

34. The method for the final product-related production and processing of plasma chemically produced mixture of halogenated polysilanes according to claim 33, wherein dependent on the number of plasma reactors or of plasma sources, in a plasma reactor polysilane mixture of predominantly low, medium and high molar weight are obtained which are led to further processing.

35. The method for the final product-related production and processing of plasma chemically produced mixture of halogenated polysilanes according to claim 33 or 34, wherein the plasma in the plasma reactor is periodically quenched by an additional electromagnetic alternating field or passes a resonator chamber tuned to the microwave source.

36. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to any one of claims 33 to 35, wherein plasma pulsing and/or additional electrical discharge and/or plasma quenching alternate in the plasma reactor.

37. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to any one of claims 33 to 36, wherein the plasma in the plasma reactor is additionally radiated with infrared light, visible light or ultraviolet light.

38. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 33 to 37, wherein the predominantly high-molecular polysilane mixtures are exposed to the separation method of the size-selective chromatography to obtain polysilane fractions with high medium molar weights. 26

39. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 33 to 38, wherein the separation fraction with predominantly low or medium molar weights is led to a direct further processing or into another distillation column.

40. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 33 to 39, wherein the polysilanes with low, medium or high molar weight obtained after the distillation or other separation methods are hydrogenated and partly hydrogenated or perhydrogenated compounds are obtained.

41. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 33 to 40, wherein the polysilanes with low, medium or high molar weight obtained after the distillation are methylated and partly methylated or permethylated organopolysilanes of the formula SiuXaMeb (a+b=2n) and Si 11 XcMed (c+d=2n+2) are obtained.

42. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 33 to 41, wherein mixtures of low molecular halogenated polysilanes are directed over a heated surface directly from the gaseous phase for the deposition of silicon and are pyrolytically decomposed there.

43. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 33 to 42, wherein liquid halogenated polysilane mixtures or their solutions are applied in suitable solvents onto deposition surfaces and are decomposed there by pyrolysis wherein silicon is deposited there.

44. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 33 to 43, wherein hydrogenated polysilanes with high purity of selected molecular weights are directed over heated surfaces in the gaseous phase and silicon is deposited on these surfaces by pyrolysis. 27

45. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 33 to 44, wherein hydrogenated polysilanes of selected molecular weights are applied onto suitable surfaces in the liquid phase or in solution and are decomposed by heating whereby silicon is deposited on these surfaces.

46. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 33 to 45, wherein silicon is deposited as layer of any thickness from mixtures of halogenated polysilanes above 400 'C or hydrogenated polysilanes above 200 'C.

47. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 33 to 45, wherein the deposited silicon layers are exposed to a heat aftertreatment.

48. Method for the final product-related production and processing of mixtures of halogenated polysilanes for the generation of silicon or silicon-based products, wherein the mixture of halogenated polysilanes is produced chemically or plasma-chemically from SiX 4 , wherein X is selected from the group consisting of F, Cl, Br, I, and H, and H 2 , wherein X is halogen, and partly or fully methylated compounds of the general formula SiuXaMeb (a+b=2n) and Si 11 XcMed (c+d=2n+2) are obtained by methylating the mixture of halogenated polysilanes or individual components thereof, wherein the produced halogenated polysilanes have a ratio of H: X<1: 5.

49. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to claim 48, wherein, dependent on the number of plasma reactors or of plasma sources, in a plasma reactor polysilane mixtures of predominantly low, medium and high molar weight are obtained which are led to further processing.

50. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to claim 48 or 49, wherein plasma pulsing and/or additional electrical discharge and/or plasma quenching alternate in the plasma reactor. 28

51. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to any one of claims 48 to 50, wherein the plasma in the plasma reactor is additionally radiated with infrared light, visible light or ultraviolet light.

52. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 48 to 51, wherein the predominantly low-molecular polysilane mixtures are led to a distillation to obtain low-molecular halogenated polysilanes, as for instance Si 2 Cl 6 and Si 3 Cl 8 , in a pure condition.

53. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 48 to 52, wherein the distillation residue with predominantly medium molar weight, as for instance Si 5 X 12 or Si 5 X 1 0 , is led to a direct further processing or is led into another distillation column.

54. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 48 to 53, wherein the polysilane mixtures with predominantly undecomposed distillable components of medium molar weight are led to a distillation to obtain individual components in pure condition and/or fractions of defined boiling ranges.

55. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 48 to 54, wherein the distillates or distillation residues with predominantly low or high molar weights are led to a direct further processing or are led into another distillation column.

56. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 48 to 55, wherein the predominantly high-molecular polysilane mixtures are exposed to the separation method of the size-selective chromatography to obtain polysilane fractions with high medium molar weights. 29

57. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 48 to 56, wherein the separation fraction with predominantly low or medium molar weights is led to a direct further processing or into another distillation column.

58. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 48 to 57, wherein the polysilanes with low, medium and high molar weight obtained after the distillation are methylated and partly methylated or permethylated organopolysilanes of the formula SinXaMeb(a+b=2n) and Si 1 XcMe(c+d=2n+2) are obtained.

59. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of the claims 48 to 58, wherein metalloid compounds and/or metalorganic compounds, as for instance methyl lithium, methyl magnesium halide, dimethyl zinc, tetramethyl silane, are used as methylation agent.

60. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 48 to 59, wherein the obtained organopolysilanes are introduced into polymers or are grafted onto the same.

61. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 48 to 60, wherein polycrystalline silicon thin layers are obtained on any carrier surfaces.

62. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 48 to 61, wherein monocrystalline silicon thin layers on any carrier surfaces are obtained.

63. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 40 to 62, wherein silicon is deposited as layer of any thickness from mixtures of halogenated polysilanes above 400 'C or hydrogenated polysilanes above 200 'C. 30

64. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 48 to 63, wherein the deposited silicon layers are exposed to a heat aftertreatment.

65. Method for the final product-related production and processing of mixtures of halogenated polysilanes for the generation of silicon or silicon-based products, wherein the mixture of halogenated polysilanes is produced plasma-chemically from SiX 4 , wherein X is selected from the group of F, Cl, Br, I, and H, and H 2 , and wherein for controlling the content of the mixture of polysilanes several plasma reactors are used in sequence for reacting SiX 4 and H 2 and the median molar mass of the mixture of polysilanes increases after having passed each plasma reactor and/or for controlling the content of the mixture of polysilanes in one plasma reactor several plasma sources are provided, said reaction mixture is fed through these sources and after each plasma source in this plasma reactor increases the median molar mass of the mixture of polysilanes, wherein the produced halogenated polysilanes have a ratio of H: X < 1:5.

66. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to claim 65, wherein, dependent on the number of plasma reactors or of plasma sources, in a plasma reactor polysilane mixtures of predominantly low, medium and high molar weight are obtained which are led to further processing.

67. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to claim 65 or 66, wherein plasma pulsing and/or additional electrical discharge and/or plasma quenching alternate in the plasma reactor.

68. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to any one of claims 65 to 67, wherein the plasma in the plasma reactor is additionally radiated with infrared light, visible light or ultraviolet light. 31

69. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of the claims 65 to 68, wherein the polysilanes with low, medium or high molar weight obtained after the distillation or other separation methods are hydrogenated and partly hydrogenated or perhydrogenated compounds are obtained.

70. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of the claims 65 to 69, wherein the hydrogenation is carried out in ethers and/or aromatic solvents.

71. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of the claims 65 to 70, wherein metal hydrides and metalloid hydrides, preferably sodium aluminum hydride or sodium boron hydride, are used as hydrogenation agents.

72. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 65 to 71, wherein the hydrogenation is preferably carried out at temperatures below 20 0 C.

73. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 65 to 72, wherein liquid halogenated polysilane mixtures or their solutions are applied in suitable solvents onto deposition surfaces and are decomposed there by pyrolysis wherein silicon is deposited there.

74. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 65 to 73, wherein hydrogenated polysilanes with high purity of selected molecular weights are directed over heated surfaces in the gaseous phase and silicon is deposited on these surfaces by pyrolysis.

75. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 65 to 74, wherein hydrogenated polysilanes of selected molecular weights are applied onto suitable surfaces in the liquid phase or in solution and are decomposed by heating whereby silicon is deposited on these surfaces. 32

76. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 65 to 75, wherein silicon is deposited as layer of any thickness from mixtures of halogenated polysilanes above 400 'C or hydrogenated polysilanes above 200 'C.

77. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 65 to 76, wherein the deposited silicon layers are exposed to a heat aftertreatment.

78. Method for the final product-related production and processing of mixtures of halogenated polysilanes for the generation of silicon or silicon based products, wherein a mixture of halogenated polysilanes produced in a plasma chemical step from SiX 4 , wherein X is selected from the group consisting of F, Cl, Br, and I, and H, and H 2 is separated into individual fractions or components in the gas or liquid phase in one or more distillation columns into individual fractions and the distillates are immediately further processed and led to further processing steps, wherein the composition of the mixture of halogenated polysilanes is controlled by the regulation of the production process and the flow of substances and wherein the produced halogenated polysilanes have a ratio of H: X < 1:5.

79. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to claim 78, wherein for the control of the composition of the polysilane mixture one or more plasma reactors are subsequently passed by the supplied reaction mixture of halogen silane and H 2 and the mean molar weight of the mixture of polysilanes increases after passage of each plasma reactor.

80. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to claim 78 or 79, wherein for controlling the composition of the polysilane mixture in a plasma reactor a plurality of plasma sources are provided and the same are passed by the reaction mixture and after each plasma source in the plasma reactor the mean molar weight of the polysilane mixture increases.

81. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to any one of claims 78 to 80, wherein the temperature of the plasma reactor or of individual components is maintained below ambient 33 temperature and the viscosity of the obtained polysilane mixture is controlled by the mixing ratio between the hydrogen content and the halogen content of the gas mixture.

82. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to any one of claims 78 to 81, wherein the plasma sources used in the plasma reactor are pulsed.

83. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to any one of claims 78 to 82, wherein the plasma in the plasma reactor is periodically quenched by an additional electromagnetic alternating field or passes a resonator chamber tuned to the microwave source.

84. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to any one of claims 78 to 83, wherein plasma pulsing and/or additional electrical discharge and/or plasma quenching alternate in the plasma reactor.

85. The method for the final product-related production and processing of plasma chemically produced mixtures of halogenated polysilanes according to any one of claims 78 to 84, wherein the plasma in the plasma reactor is additionally radiated with infrared light, visible light or ultraviolet light.

86. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 85, wherein the predominantly low-molecular polysilane mixtures are led to a distillation to obtain low-molecular halogenated polysilanes, as for instance Si 2 Cl 6 and Si 3 Cl 8 , in a pure condition.

87. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 86, wherein the distillation residue with predominantly medium molar weight, as for instance Si 5 X12 or Si 5 X 10 , is led to a direct further processing or is led into another distillation column. 34

88. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 87, wehrein the polysilane mixtures with predominantly undecomposed distillable components of medium molar weight are led to a distillation to obtain individual components in pure condition and/or fractions of defined boiling ranges.

89. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 88, wherein the distillates or distillation residues with predominantly low or high molar weights are led to a direct further processing or are led into another distillation column.

90. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 89, wherein the predominantly high-molecular polysilane mixtures are exposed to the separation method of the size-selective chromatography to obtain polysilane fractions with high medium molar weights.

91. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 90, wherein the separation fraction with predominantly low or medium molar weights is led to a direct further processing or into another distillation column.

92. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to one of claims 78 to 91, wherein the polysilanes with low, medium or high molar weight obtained after the distillation or other separation methods are hydrogenated and partly hydrogenated or perhydrogenated compounds are obtained.

93. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 92, wherein the hydrogenation is carried out in ethers and/or aromatic solvents.

94. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 93, wherein metal hydrides and metalloid hydrides, preferably sodium aluminum hydride or sodium boron hydride, are used as hydrogenation agents. 35

95. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 94, wherein the hydrogenation is preferably carried out at temperatures below 20 0 C.

96. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 95, wherein the polysilanes with low, medium and high molar weight obtained after the distillation are methylated and partly methylated or permethylated organopolysilanes of the formula SinXaMeb(a+b=2n) and Si 1 XcMe(c+d=2n+2) are obtained.

97. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 96, wherein metalloid compounds and/or metalorganic compounds, as for instance methyl lithium, methyl magnesium halide, dimethyl zinc, tetramethyl silane, are used as methylation agent.

98. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 97, wherein the obtained organopolysilanes are introduced into polymers or are grafted onto the same.

99. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 98, wherein mixtures of low molecular halogenated polysilanes are directed over a heated surface directly from the gaseous phase for the deposition of silicon and are pyrolytically decomposed there.

100. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 99, wherein liquid halogenated polysilane mixtures or their solutions are applied in suitable solvents onto deposition surfaces and are decomposed there by pyrolysis wherein silicon is deposited there.

101. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of the claims 78 to 100, wherein hydrogenated polysilanes with high purity of selected molecular weights are directed over heated surfaces in the gaseous phase and silicon is deposited on these surfaces by pyrolysis. 36

102. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 101, wherein hydrogenated polysilanes of selected molecular weights are applied onto suitable surfaces in the liquid phase or in solution and are decomposed by heating whereby silicon is deposited on these surfaces.

103. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 102, wherein amorphous silicon thin layers on any carrier surfaces are obtained as final product.

104. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 103, wherein polycrystalline silicon thin layers are obtained on any carrier surfaces.

105. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 104, wherein monocrystalline silicon thin layers on any carrier surfaces are obtained.

106. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 105, wherein silicon is deposited as layer of any thickness from mixtures of halogenated polysilanes above 400 'C or hydrogenated polysilanes above 200 'C.

107. The method for the final product-related production and processing of mixtures of halogenated polysilanes according to any one of claims 78 to 106, wherein the deposited silicon layers are exposed to a heat aftertreatment. Spawnt Private S.a.r.l. Patent Attorneys for the Applicant/Nominated Person SPRUSON & FERGUSON