Solid source and method for the synthesis of silicon-containing precursors for chemical vapor deposition

Abstract

The present document described a solid source and a method for synthesis of silicon-containing precursors for chemical vapor deposition. The solid source comprises a solid polysilane; an energy coupling agent distributed in the solid polysilane; and hydrogen, mixed with the solid polysilane and the energy coupling agent distributed in the solid polysilane, in a necessary amount to satisfy a hydrogen deficiency during a hydrogenolysis reaction.

Claims

1. A solid source for synthesis of silicon-containing precursors for chemical vapor deposition, the solid source comprising: a solid polysilane; an energy coupling agent distributed in the solid polysilane; and hydrogen, mixed with the solid polysilane and the energy coupling agent distributed in the solid polysilane, in a necessary amount to satisfy a hydrogen deficiency during a hydrogenolysis reaction.

2. The solid source of claim 1, further comprising a hydrogen-carrier mixed with the solid polysilane and the energy coupling agent distributed in the solid polysilane, the hydrogen-carrier comprising the hydrogen in the necessary amount to satisfy the hydrogen deficiency during the hydrogenolysis reaction.

3. The solid source of claim 2, further comprising a hydrogenation catalyst mixed with at least one of the solid polysilane, the energy coupling agent and the hydrogen-carrier.

4. The solid source of claim 2, wherein at least one of the hydrogen-carrier and the energy coupling agent comprises at least one of: a graphite material, a fullerene material, a graphene material, an activated carbon material, a carbon-metal complex material, metal complex material, ceramic material, a zeolite material, a glass microsphere material, a glass capillary or filament material, a silicon carbide material, a silicon-metal complex material, an electrically conductive material that can be heated by at least one of: induction, radio-frequency, absorption radiation and microwave radiation and a nanotube material.

5. The solid source of claim 3, wherein the hydrogenation catalyst comprises at least one of: cobalt (Co), nickel (Ni), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), titanium (Ti), zirconium (Zr), hafnium (Hf), an oxide of a Ziegler-Nata catalyst and a metal-free catalyst.

6. The solid source of claim 2, wherein the hydrogen contained in the hydrogen-carrier is from about 0.01 to about 10 times a stoichiometric amount necessary to satisfy the hydrogenolysis reaction.

7. The solid source of claim 6, wherein the solid polysilane and the hydrogen are mixed in a stoichiometric ratio solid polysilane/hydrogen of about 0.1 to about 10.

8. The solid source of claim 2, wherein the hydrogen-carrier is in one of: a gel state and a solid state.

9. The solid source of claim 1, further comprising at least one of: an electrically conductive material and a thermally conductive material mixed with the solid polysilane.

10. The solid source of claim 9, wherein the at least one of: the electrically conductive material and the thermally conductive material comprises at least one of: a powder capable of RF coupling, flakes capable of RF coupling, granules capable of RF coupling, chunks capable of RF coupling, a powder capable of IR coupling, flakes capable of IR coupling, granules capable of IR coupling, chunks capable of IR coupling, a powder capable of UV coupling, flakes capable of UV coupling, granules capable of UV coupling and chunks capable of UV coupling.

11. The solid source of claim 1, wherein the weight of the solid source is between about 0.1 g to about 10 kg.

12. The solid source of claim 1, wherein the solid polysilane comprises at least one of: a polymethylsilane, a polydimethylsilane, a polyvinylsilane, a polyhydridosilane and a polyphenylsilane.

13. A method for synthesis of a solid source for the production of silicon-containing precursors for vapor chemical deposition, the method comprising: mixing a solid polysilane and an energy coupling agent distributed in the solid polysilane with a necessary amount of hydrogen to satisfy a hydrogen deficiency during a hydrogenolysis reaction.

14. The method of claim 13, wherein mixing the solid polysilane and the energy coupling agent distributed in the solid polysilane with a necessary amount of hydrogen to satisfy the hydrogen deficiency during the hydrogenolysis reaction comprises mixing the solid polysilane and the energy coupling agent distributed in the solid polysilane with a hydrogen-carrier comprising the necessary amount of hydrogen to satisfy the hydrogen deficiency during the hydrogenolysis reaction.

15. The method of claim 14, further comprising mixing a hydrogenation catalyst with at least one of: the solid polysilane, the energy coupling agent and the hydrogen-carrier, the hydrogenation catalyst comprising at least one of: cobalt (Co), nickel (Ni), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), titanium (Ti), zirconium (Zr), hafnium (Hf), an oxide of a Ziegler-Nata catalyst and a metal-free catalyst.

16. The method of claim 14, wherein the mixing the solid polysilane and the energy coupling agent distributed in the solid polysilane with the hydrogen-carrier comprises one of: pressing and compacting the solid polysilane and the energy coupling agent distributed in the solid polysilane with the hydrogen-carrier.

17. The method of claim 16, wherein the one of: pressing and compacting occurs at a pressure of between about 10.sup.5 torr and 100 atm.

18. The method of claim 13, wherein the hydrogenolysis reaction has a reaction temperature of between about 100 C. and about 400 C.

19. The method of claim 18, further comprising controlling the reaction temperature of the hydrogenolysis reaction for sequentially satisfy the hydrogen deficiency during the hydrogenolysis reaction.

20. The method of claim 13, further comprising mixing at least one of: an electrically conductive material and a thermally conductive material with at least one of: the solid polysilane, the energy coupling agent and the hydrogen.

21. The method of claim 20, further comprising mixing the electrically conductive material and the thermally conductive material with the at least one of: the solid polysilane, the energy coupling agent and the hydrogen.

Description

DETAILED DESCRIPTION

(1) In embodiments there are disclosed solid sources and methods for the synthesis of silicon-containing precursors for chemical vapor deposition.

(2) According to an embodiment, there is provided a solid source for synthesis of silicon-containing precursors for chemical vapor deposition. The solid source includes a solid polysilane, an energy coupling agent distributed in the solid polysilane and hydrogen, mixed with the solid polysilane and the energy coupling agent distributed in the solid polysilane, in a necessary amount to satisfy a hydrogen deficiency during a hydrogenolysis reaction.

(3) According to another embodiment, the solid source may further includes a hydrogen-carrier mixed with the solid polysilane and the energy coupling agent distributed in the solid polysilane. The hydrogen-carrier and/or the energy coupling agent (which may be a susceptor) are for liberating the necessary amount of hydrogen to satisfy the hydrogen deficiency during the hydrogenation reaction. Thus, the solid polysilane and the energy coupling agent of the solid source may be compressed and/or mixed with the hydrogen-carrier and/or with hydrogen molecules found in void spaces provided within the solid polysilane and/or the energy coupling agent in order to satisfy the hydrogen deficiency during the hydrogenolysis reaction.

(4) According to another embodiment, the energy coupling agent and/or the hydrogen-carrier may include, without limitation, a graphite material, a fullerene material, a graphene material, an activated carbon material, a carbon-metal complex material, a zeolite material, a glass microsphere material, a glass capillary or filament material, a silicon carbide material, a silicon-metal complex material, an electrically conductive material that can be heated by induction, radio-frequency, ultraviolet or infrared radiation and/or microwave radiation and/or a nanotube material, and the like.

(5) According to another embodiment, the hydrogen-carrier (or the energy coupling agent) may further include, without limitation, metal complexes and/or ceramic materials, and the like.

(6) According to another embodiment, the solid source may further include a hydrogenation catalyst mixed with the solid polysilane and/or the hydrogen-carrier (or hydrogen) and/or the energy coupling agent.

(7) According to another embodiment, the hydrogenation catalyst may include, without limitation, cobalt (Co), nickel (Ni), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), titanium (Ti), zirconium (Zr), hafnium (Hf), an oxide of a Ziegler-Nata catalyst and/or a metal-free catalyst, and the like.

(8) According to another embodiment, the hydrogenation catalyst may be a complex of any of the above-noted metals which may include, without limitation, metallocene complexes and the like.

(9) According to another embodiment, the hydrogenation catalyst can be designed for hydro-amination, hydro-phosphorilation, and/or hydro-boration of the solid polysilane.

(10) According to another embodiment, the hydrogen catalyst may further include, without limitation, any common catalysts used in general organic synthesis, particular design for hydrogenation reactions in terms of substrate, granulation, activation, and the like.

(11) More particularly and according to another embodiment, there is provided a solid source for the synthesis of a large series of organosilanes. More particularly, there is provided a solid source for the synthesis of a large series of organosilanes with the formula R.sub.2n+2xSi.sub.nH.sub.x, where RC.sub.nH.sub.2n+1, n=1 . . . 3 and x=2 . . . 6.

(12) According to a further embodiment, the solid source may include an electrically and/or thermally conductive material and/or a thermal conductive material.

(13) According to another embodiment, the electrically and/or thermally conductive material may be, without limitation, a powder, flakes, granules, chunks, and the like capable of RF coupling or any other energy coupling using induction, radio-frequency, ultraviolet or infrared radiation and/or microwave radiation and the like.

(14) According to another embodiment, the thermally conductive material may be, without limitation, powder, flakes, granules, chunks and the like.

(15) It is to be noted that using the solid source as described, the efficiency of silicon-containing precursor formation can be increased from a usual 30% to values higher than 50% of the theoretical yield.

(16) According to another embodiment, the solid source described above, may be best suited for an efficient synthesis of methylsilanes with the formulae (CH.sub.3).sub.4xSiH.sub.x which may be used as precursors for, without limitation, the industrial production of a large variety of silicon-based ceramic films, including, but not limited to, silicon carbide, silicon carbonitride, silicon nitride, silicon oxicarbide, silicon oxinitride, silicon oxicarbonitride. These films may be widely used as passive and active films in the semiconductor industry. The films may also be utilized as protective and refractive coatings in industries such as the automotive, the aeronautical, and the weapon industries.

(17) The amount of hydrogen contained in the hydrogen-carrier may be calculated to ensure from about 1% to about 10 times the stoichiometric amount necessary to synthesize the hydrogenated monomer, which may be equivalent of 2 hydrogen atoms for each broken SiSi bond.

(18) According to another embodiment, the solid polysilane may be, without limitation, polymethylsilane, polydimethylsilane, polyvinylsilane, polyhydridosilane, polyphenylsilane, any copolymer as defined above, which includes poly(methyl)dimethylsilane, and the like.

(19) According to another embodiment, R (R.sub.2n+2xSi.sub.nH.sub.x, where RC.sub.nH.sub.2n+1) may be an organic substituent.

(20) According to another embodiment, the organic substituent R may be, without limitation, a nonsaturated group containing any of the elements carbon (C), hydrogen (H), silicium (Si), nitrogen (N), bore (B), phosphor (P), aluminum (Al), antimony (Sb), arsenic (As), gallium (Ga), indium (In), titanium (Ti), zirconium (Zr) and/or sulfur (S), and the like.

(21) According to another embodiment, the hydrogen-carrier may be in, without limitation, an amorphous form, a vitrified form, a crystalline form, any suitable combination and the like.

(22) According to another embodiment, the hydrogen-carrier may be any electrically conductive material that can be heated via induction, illumination or radio-frequency.

(23) According to another embodiment, the hydrogen-carrier may be any material that can be heated via absorption of any radiation.

(24) According to another embodiment, the hydrogen-carrier may include a material where the hydrogen-storage capacity of the material may be enhanced via metal doping, or induced polarization via electric or magnetic fields.

(25) According to another embodiment, the hydrogenation catalyst may be an oxide (oxide of cobalt (Co), nickel (Ni), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), titanium (Ti), zirconium (Zr), hafnium (Hf), an oxide of a Ziegler-Nata catalyst and/or a metal-free catalyst) such as, without limitation, Al.sub.2O.sub.3, TiO.sub.2, any suitable combination and the like.

(26) According to another embodiment, the solid polysilane of the solid source may be a polydimethylsilane.

(27) According to another embodiment, the solid polysilane of the solid source may be a polymethylsilane.

(28) According to another embodiment, the solid polysilane of the solid source may be a copolymer methyl-dimethyl-silane.

(29) According to another embodiment, the nickel (Ni)-hydrogenation catalyst may be in a form such as, without limitation, a Raney form, a Urushibara form and the like.

(30) According to another embodiment, the metal hydrogenation catalyst may be provided on a support.

(31) According to another embodiment, there is provided a method for synthesis of the solid source for the production of silicon-containing precursors for vapor chemical deposition. The method includes mixing the solid polysilane and the energy coupling agent distributed in the solid polysilane with the necessary amount of hydrogen to satisfy the hydrogen deficiency during the hydrogenolysis reaction.

(32) According to another embodiment, the solid source may be obtained by pressing the mixture of the solid polysilane (with the energy coupling agent distributed in the solid polysilane) with the hydrogen-carrier which is designed to liberate the necessary amount of hydrogen to satisfy the hydrogen deficiency required for the regeneration of the monomer (i.e., R.sub.2n+2xSi.sub.nH.sub.x) via the hydrogenolysis reaction. As described above, the hydrogen-carrier may be based on C-containing compounds which are known for their capacity for storing hydrogen in molecular or atomic form. As mentioned above, the C-containing compound may include, without limitation, graphite materials, fullerene materials, graphene materials, activated carbon materials, carbon-metal complex materials, zeolite materials, glass microsphere materials, glass capillary or filament materials, silicon carbide materials, silicon-metal complex materials, electrically conductive material that can be heated by induction, radio-frequency, absorption radiation and/or microwave radiation and/or nanotube materials, and the like.

(33) According to another embodiment, the method may further include the step of mixing the hydrogenation catalyst which may include, without limitation, cobalt (Co), nickel (Ni), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), titanium (Ti), zirconium (Zr), hafnium (Hf), an oxide of a Ziegler-Nata catalyst and/or a metal-free catalyst and/or any suitable combination, and the like, with the solid polysilane, the energy coupling agent and/or the hydrogen-carrier.

(34) According to another embodiment, the step of mixing the solid polysilane (and the energy coupling distributed in the solid polysilane) with the hydrogen-carrier may include the step of mixing a mixture of solid polysilanes (and the energy coupling distributed in the solid polysilane) with the hydrogen-carrier for the production of precursors for CVD.

(35) According to another embodiment, the method may include the step a) of providing a solid polymeric source which includes the polysilane, or a mixture which includes at least one polysilane specie. The method may further includes the step b) of providing the hydrogen-carrier. The hydrogenation reaction may be thermodynamically favored at low temperatures (the uncertainty on the value of free enthalpy of polydimethylsilane is still high at this time) but extrapolating the results of the equilibrium state in the systems disilane-hydrogen, trisilane-hydrogen and the corresponding methyl-substituted silanes, the temperature range of 100 C. to about 400 C. is adequate for advancing the transformation of the polydimethylsilane into dimethylsilane from the previously obtained yield of 30% to higher values (as shown in examples 1 to 8 below).

(36) According to a further embodiment, the hydrogen-carrier may bring to the system, instead of hydrogen, the following compounds in adsorbed, absorbed, chemically and/or physically bound, or included state, without limitation, NH.sub.3, N.sub.2H.sub.4, PH.sub.3, BH.sub.3, B.sub.2H.sub.6 and the like.

(37) According to another embodiment, the method may further include the step c) of providing/mixing the hydrogenation catalyst mentioned above with the solid polysilane, energy coupling agent and/or the hydrogen-carrier (or hydrogen). According to another embodiment, the method may further include the step d) of providing/mixing an electrically and/or thermally conductive material with the solid polysilane, the energy coupling agent, the hydrogen-carrier and/or the hydrogenation catalyst.

(38) According to another embodiment, the method may further include the step e) of providing/mixing a thermally conductive material with the solid polysilane, the energy coupling agent, the hydrogen-carrier and/or the hydrogenation catalyst.

(39) According to another embodiment, the thermally conductive material may be mixed with the solid polysilane.

(40) According to another embodiment, the method may further include the step f) of compacting, isostatically or unidirectional, the solid polysilane (provided in step a), the hydrogen-carrier (provided in step b), the hydrogenation catalyst (provided in step c), the electrically and/or thermally conductive material (provided in step d) and/or the thermally conductive material (provided in step e) in order to produce a self-sustainable block.

(41) According to an embodiment, the mass of the obtained self-sustainable block may between about 0.1 g to about 10 kg.

(42) According to another embodiment, the method may further include the step of mixing the solid polysilane and the hydrogen-carrier in a stoichiometric ratio solid polysilane/hydrogen of about 0.1 to about 10.

(43) According to another embodiment, the method may further include the step of mixing the solid polysilane and the electrically and/or thermally conductive material in a stoichiometric ratio solid polysilane/hydrogen of about 0.1 to about 10.

(44) According to another embodiment, the method may further include the step of providing the electrically and/or thermally conductive material in a hydrogen-enriched form. Hydrogen may be physically and/or chemically bound, molecular and/or atomic, in neutral and/or ionic form.

(45) According to another embodiment, the method may further include the step of mixing the solid polysilane, the hydrogen-carrier and the hydrogenation catalyst, where the mass ratios between any two components is from about 0.1 to about 10.

(46) According to another embodiment, the method may further include the step of heating the mixture (i.e., the solid polysilane with its distributed energy coupling agent mixed with hydrogen or hydrogen-carrier and the hydrogenation catalyst, the electrically and/or thermally conductive material) at a temperature higher than about 100 C. and lower than about 700 C. so that the breaking of the SiSi bond of the polymer (i.e., the solid polysilane) is simultaneous or consecutive to the liberation of reactive hydrogen from the hydrogen-carrier. The method allows the reaction to occur below 400 C., to avoid formation of undesired byproducts. However, theory and reality may be different, especially when the weight of the solid source is from 0.5 g to 1 kg. Accordingly, the temperature of the reaction is such that it does not reduce drastically the formation of dimethylsilane. This step may provide that the reaction of the polymeric fragments of the solid polysilane with hydrogen is carried under a hydrogen-rich atmosphere in the presence of the hydrogenation catalyst.

(47) According to another embodiment, the method described above may further include a step of controlling the temperature of the hydrogenolysis reaction for sequentially satisfying the hydrogen deficiency during the hydrogenolysis reaction. Indeed, instead of decomposing totality of the solid source under the hydrogenolysis reaction, the solid source may be decomposed partially during different stages of the hydrogenolysis reaction, by controlling the temperature of reaction. This sequential reaction is possible due to the fact that the solid source, which is decomposed under hydrogenolysis reaction, is decomposed at a lower temperature (i.e., from about 100 C. to about 400 C.), and to the rapidity of the induction heating of the solid source (i.e., which is possible because of the mixture of solid polysilane and the hydrogen-carrier). Therefore, the synthesis of gaseous silicon-based precursors may be performed by the reaction only when there is a need, by controlling the temperature of the reaction. Some advantages of the sequential synthesis is that the stockade may be performed under a solid form, and not under the gaseous form, which is easier to stock.

(48) The method may render both kinetic and thermodynamic conditions favorable for the reaction between the polymeric fragments of the solid polysilane resulted from the scission of the SiSi bonds with hydrogen, generating the hydrogenated monomer (i.e., if the polymer used is polydimethylsilane, dimethylsilane is generated efficiently). Under these conditions, the efficiency is largely favored over the alternative insertion of the R.sub.3Si fragments in the CH bonds (i.e., reaction known as the Kumada rearrangement) that leads to the formation of carbosilane species.

(49) One of the differences between the solid sources and methods as described above and the solid sources and methods of the prior art may result in the in situ addition of graphite (i.e., energy coupling agent), in intimate mixture with or distributed within the solid source. There are at least two advantages related to the methods as described above: a) the graphite susceptor (i.e., energy coupling agent or RF susceptor) mixed with the solid polysilane source allows in situ use of inductive heating, therefore more efficient, more homogeneous, faster rate and better control of the heat input required for the reaction producing the gaseous precursors; b) graphite is one of the most promising supports for hydrogen storage, and hydrogen deficiency of the source itself drastically limits the extent of the hydrogenolysis reaction required to produce the CVD-precursors (i.e., SiXtron: 220 L vs. the 250 L required by industry standardse.g., SunTech Corp.).

(50) The methods as described above for the generation of the CVD-precursors aims at total compatibility with the procedure used today by the main manufacturers of solar cells. According to the methods described above, it is possible to deliver faster, more precursors for the films, and in a more energetically-efficient way.

(51) According to another embodiment, graphene (i.e., thin layers of graphite) may be some of the best candidates for the method as described above, due to their capacity of storage and cheap cost of production.

(52) According to another embodiment, if SiC can be used as a susceptor, then the methods as described above may allow synthesizing SiC from polydimethylsilane (PDMS), in the same way as graphite. It would be expected in this case that the C-level of the film in the SiC-susceptor case would be lower.

(53) According to another embodiment, the mixture of the solid polysilane, the energy coupling agent and the hydrogen-carrier (hydrogen) may be heated. The efficiency of this solid source is the result of at least improved thermodynamic conditions.

(54) According to another embodiment, the solid polysilane, the energy coupling agent, the hydrogen-carrier (or hydrogen) and the hydrogenation catalyst, when mixed together, are heated. The efficiency of this solid source is the result of at least the improvement of both thermodynamic (i.e., in relationship with excess hydrogen) and kinetic (i.e., in relationship with catalysis effect) conditions.

(55) According to another embodiment and as mentioned, the hydrogen-carrier may be an electrically conductive material capable of storing hydrogen. The hydrogen-carrier may include, without limitation, graphite, graphite nanofibers, graphene (i.e., graphene is being used to soak up hydrogen and store it efficiently), fullerene, carbon nano tubes, activated carbon, carbon-metal complexes, zeolites, glass microspheres, any solid nanostructured material capable of adsorbing and/or absorbing hydrogen, either by physical (i.e., van der Waals) or chemical bonding in covalent, polar or ionic form, and the like.

(56) According to another embodiment, the hydrogen-carrier may be an electrically conductive material capable of storing a large amount of hydrogen, which includes, without limitation, functionalized graphite, graphene, fullerene and the like.

(57) According to another embodiment, the hydrogen-carrier may be any mixture of, without limitation, hydrogen-filled graphite, graphene, fullerene, carbon nanotubes, silicon carbide, silicon or carbon-metal complexes, glass microspheres, glass capillaries or filaments, activated carbon and/or functionalized derivatives and the like.

(58) According to another embodiment, the hydrogenation catalyst may be provided in tandem with discriminatory poisons for the hydrogenation of Si-, Ti-, Zr- Hf-, and/or C-centers.

(59) According to another embodiment, for obtaining the solid source, the method may further include the step of compacting the solid polysilane using pressure, either monodirectional and/or isostatical methods.

(60) According to another embodiment, the method may further include the step of compacting the solid polysilane with the hydrogen-carrier and/or the electrically and/or thermally conductive material.

(61) According to another embodiment, the method may further include the step of compacting the solid polysilane with the hydrogen-carrier, the hydrogenation catalyst and/or the electrically and/or thermally conductive material.

(62) According to another embodiment, the temperature of the hydrogenation reaction is in the range of from about 100 C. to about 700 C. and more particularly from about 100 C. to about 400 C.

(63) According to another embodiment, the energy input required for the hydrogenation reaction may be provided by, in conjunction with RF or not, without limitation, thermal resistance, conduction, infrared radiation, UV radiation in the 100-400 nm range, induction heating, microwave radiation, plasma and the like, or any combination of the above, in any proportion.

(64) According to another embodiment, the pressure obtained during the hydrogenation reaction is in the range of from about 10.sup.5 torr to about 100 atm.

(65) According to another embodiment, the method may further include de step of enriching the solid polysilane with, without limitation, solid, liquid and/or gaseous species which contains N, B, P, Al, Sb, Ga, which includes NH.sub.3, PH.sub.3, B.sub.2H.sub.6, N.sub.2H.sub.4, CH.sub.3NH.sub.2, hydrazine, ethylenediamine and the like.

(66) The method described above may provide a plurality of improvements, such as, without limitation, an extremely rapid heating, a cost-effective application, a selectively localized heating, and a high reproducibility of the method. These improvements are permitted by the presence of the distributed susceptors in the solid polysilane.

(67) The incorporation of the hydrogenation catalyst (i.e., the component C of the solid polysilane) allows the hydrogenation reaction to occur in a temperature range preventing a large advancement of the Kumada rearrangement leading to carbosilane byproducts.

(68) The presence of a partial pressure molecular hydrogen (hydrogen molecular alone or hydrogen-carrier providing the hydrogen molecular) in the solid polysilane leads thermodynamically the hydrogenation of the nonsaturated SiSi bonds produced by thermal decomposition in disilane and trisilane compounds (i.e., no thermodynamic data for polymeric species are yet available in the open literature). The thermodynamic predictions for the hydrogenation of the thermally produced R.sub.3Si fragments by reaction with H.sub.2(g) show favorable bond saturation of the thermally fragmented species via terminal H.

(69) According to a further embodiment, there is provided an apparatus (not shown) for synthesis of silicon-containing precursors for chemical vapor deposition. The apparatus includes a quartz reactor chamber which contains a solid source which includes the solid polysilane mixed with the graphite susceptors (i.e., hydrogen carrier) and/or the hydrogenation catalyst. The apparatus further includes an RF generator which powers a copper inductor surrounding the quartz reactor chamber.

(70) According to another embodiment, the quartz reactor chamber which contains the solid polysilane, intimately mixed with the energy coupling agent, such as a graphite susceptor, and/or the hydrogenation catalyst may replace the steel-made reactor of the prior art, containing only the polysilane source).

(71) The solid sources and methods described above provides an improved heat transfer (i.e., fast, massive, homogeneous), a correction of a chemical imbalance (i.e., more efficient precursor-production, improved compatibility with existent industrial processes, increased application-potential).

(72) The present invention will be more readily understood by referring to the following examples which are given to illustrate the invention rather than to limit its scope.

Example 1

Thermodynamic Equilibrium Calculation for the Hydrogenation of the Thermally Dissociated SiSi Bond

(Generic Example: Si2H6 (g)+H2 (g)=>2 SiH4(g)

(73) Example 1 shows the effect of initial hydrogen content on the equilibrium concentration of hydrogenated monomer at P=1 atm and T=400 C.

(74) TABLE-US-00001 Initial State Equilibrium State Initial Equilibrium mole mole State State fraction fraction Pressure (atm) 1.3158E+00 SI2H6 1.0000E+00 5.9201E10 Temperature (K) 6.7315E+02 H2 0.0000E+00 9.9991E01 Volume (cm.sup.3/g) 6.7470E+02 SIH4 0.0000E+00 8.7478E05 Enthalpy (erg/g) 1.9234E+10 Internal Energy (erg/g) 1.8334E+10 Entropy (erg/g K) 5.6497E07 Initial State Equilibrium State Initial Equilibrium mole mole State State fraction fraction Pressure (atm) 1.3158E+00 SI2H6 8.3333E01 6.7772E01 Temperature (K) 6.7315E+02 H2 1.6667E01 1.1056E02 Volume (cm.sup.3/g) 8.0443E+02 SIH4 0.0000E+00 3.1122E01 Enthalpy (erg/g) 1.9460E+10 Internal Energy (erg/g) 1.8388E+10 Entropy (erg/g K) 6.1708E+07 Initial State Equilibrium State Initial Equilibrium mole mole State State fraction fraction Pressure (atm) 1.3158E+00 SI2H6 7.1429E01 4.6848E01 Temperature (K) 6.7315E+02 H2 2.8571E01 3.9908E02 Volume (cm.sup.3/g) 9.3250E+02 SIH4 0.0000E+00 4.9161E01 Enthalpy (erg/g) 1.9684E+10 Internal Energy (erg/g) 1.8440E+10 Entropy (erg/g K) 6.6531E+07 Initial State Equilibrium State Initial Equilibrium mole mole State State fraction fraction Pressure (atm) 1.3158E+00 SI2H6 6.2500E01 3.3089E01 Temperature (K) 6.7315E+02 H2 3.7500E01 8.0890E02 Volume (cm.sup.3/g) 1.0589E+03 SIH4 0.0000E+00 5.8822E01 Enthalpy (erg/g) 1.9904E+10 Internal Energy (erg/g) 1.8492E+10 Entropy (erg/g K) 7.1193E+07 Initial State Equilibrium State Initial Equilibrium mole mole State State fraction fraction Pressure (atm) 1.3158E+00 SI2H6 5.5556E01 2.3978E01 Temperature (K) 6.7315E+02 H2 4.4444E01 1.2867E01 Volume (cm.sup.3/g) 1.1838E+03 SIH4 0.0000E+00 6.3154E01 Enthalpy (erg/g) 2.0122E+10 Internal Energy (erg/g) 1.8543E+10 Entropy (erg/g K) 7.5740E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 5.0000E01 9.6862E01 1.7872E01 3.4622E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 5.0000E01 3.1383E02 1.7872E01 1.1218E02 Volume (cm.sup.3/g) 1.3071E+03 1.3071E+03 SIH4 0.0000E+00 0.0000E+00 6.4257E01 6.4257E01 Enthalpy (erg/g) 2.0337E+10 1.8410E+10 Internal Energy (erg/g) 1.8594E+10 1.6668E+10 Entropy (erg/g K) 8.0194E+07 7.9996E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 3.3333E01 9.3914E01 5.9224E02 1.6686E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 6.6667E01 6.0857E02 3.9256E01 3.5835E02 Volume (cm.sup.3/g) 1.9009E+03 1.9009E+03 SIH4 0.0000E+00 0.0000E+00 5.4822E01 7.9730E01 Enthalpy (erg/g) 2.1372E+10 1.8982E+10 Internal Energy (erg/g) 1.8838E+10 1.6448E+10 Entropy (erg/g K) 1.0137E+08 1.0131E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 2.5000E01 9.1141E01 2.8671E02 1.0453E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 7.5000E01 8.8590E02 5.2867E01 6.2447E02 Volume (cm.sup.3/g) 2.4597E+03 2.4597E+03 SIH4 0.0000E+00 0.0000E+00 4.4266E01 8.3303E01 Enthalpy (erg/g) 2.2347E+10 1.9850E+10 Internal Energy (erg/g) 1.9067E+10 1.6570E+10 Entropy (erg/g K) 1.2106E+08 1.2127E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 2.0000E01 8.8527E01 1.6831E02 7.4498E02 Temperature (K) 6.7315E+02 6.7315E+02 H2 8.0000E01 1.1473E01 6.1683E01 8.8463E02 Volume (cm.sup.3/g) 2.9865E+03 2.9865E+03 SIH4 0.0000E+00 0.0000E+00 3.6634E01 8.3704E01 Enthalpy (erg/g) 2.3265E+10 2.0756E+10 Internal Energy (erg/g) 1.9284E+10 1.6775E+10 Entropy (erg/g K) 1.3953E+08 1.3996E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 1.6667E01 8.6058E01 1.1056E02 5.7086E02 Temperature (K) 6.7315E+02 6.7315E+02 H2 8.3333E01 1.3942E01 6.7772E01 1.1338E01 Volume (cm.sup.3/g) 3.4838E+03 3.4838E+03 SIH4 0.0000E+00 0.0000E+00 3.1122E01 8.2953E01 Enthalpy (erg/g) 2.4133E+10 2.1646E+10 Internal Energy (erg/g) 1.9488E+10 1.7001E+10 Entropy (erg/g K) 1.5690E+08 1.5752E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 1.4286E01 8.3724E01 7.8145E03 4.5798E02 Temperature (K) 6.7315E+02 6.7315E+02 H2 8.5714E01 1.6276E01 7.2210E01 1.3712E01 Volume (cm.sup.3/g) 3.9542E+03 3.9542E+03 SIH4 0.0000E+00 0.0000E+00 2.7009E01 8.1708E01 Enthalpy (erg/g) 2.4953E+10 2.2504E+10 Internal Energy (erg/g) 1.9681E+10 1.7232E+10 Entropy (erg/g K) 1.7330E+08 1.7406E+08

Example 2

Thermodynamic Equilibrium Calculation for the Hydrogenation of the Thermally Dissociated SiSi Bond

Generic Example: Si2H6 (g)+H2 (g)=>2 SiH4(g)

(75) Example 2 shows the effect of initial hydrogen content on the equilibrium concentration of hydrogenated monomer at P=1 atm and T=300 C.

(76) TABLE-US-00002 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 4.0589E+01 SI2H6 1.0000E+00 1.0000E+00 4.1991E11 1.2954E09 Temperature (K) 5.7315E+02 5.7315E+02 H2 0.0000E+00 0.0000E+00 9.9997E01 9.9951E01 Volume (cm.sup.3/g) 5.7447E+02 5.7447E+02 SIH4 0.0000E+00 0.0000E+00 3.1077E05 4.9489E04 Enthalpy (erg/g) 1.7274E+10 3.9778E+10 Internal Energy (erg/g) 1.6508E+10 1.6151E+10 Entropy (erg/g K) 5.3349E+07 5.8929E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 8.3333E01 9.9356E01 6.7328E01 8.0274E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 1.6667E01 6.4383E03 6.6166E03 2.5560E04 Volume (cm.sup.3/g) 6.8493E+02 6.8493E+02 SIH4 0.0000E+00 0.0000E+00 3.2010E01 1.9701E01 Enthalpy (erg/g) 1.7419E+10 1.6875E+10 Internal Energy (erg/g) 1.6506E+10 1.5962E+10 Entropy (erg/g K) 5.8429E+07 5.8620E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 7.1429E01 9.8721E01 4.5442E01 6.2804E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 2.8571E01 1.2794E02 2.5845E02 1.1573E03 Volume (cm.sup.3/g) 7.9397E+02 7.9397E+02 SIH4 0.0000E+00 0.0000E+00 5.1974E01 3.7080E01 Enthalpy (erg/g) 1.7562E+10 1.6539E+10 Internal Energy (erg/g) 1.6504E+10 1.5480E+10 Entropy (erg/g K) 6.3123E+07 6.3202E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 6.2500E01 9.8093E01 3.0718E01 4.8212E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 3.7500E01 1.9069E02 5.7184E02 2.9079E03 Volume (cm.sup.3/g) 9.0163E+02 9.0163E+02 SIH4 0.0000E+00 0.0000E+00 6.3563E01 5.1497E01 Enthalpy (erg/g) 1.7704E+10 1.6282E+10 Internal Energy (erg/g) 1.6502E+10 1.5080E+10 Entropy (erg/g K) 6.7658E+07 6.7588E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 5.5556E01 9.7473E01 2.1000E01 3.6845E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 4.4444E01 2.5265E02 9.8887E02 5.6215E03 Volume (cm.sup.3/g) 1.0079E+03 1.0079E+03 SIH4 0.0000E+00 0.0000E+00 6.9111E01 6.2593E01 Enthalpy (erg/g) 1.7843E+10 1.6116E+10 Internal Energy (erg/g) 1.6499E+10 1.4772E+10 Entropy (erg/g K) 7.2079E+07 7.1898E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 5.0000E01 9.6862E01 1.4715E01 2.8506E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 5.0000E01 3.1383E02 1.4715E01 9.2360E03 Volume (cm.sup.3/g) 1.1129E+03 1.1129E+03 SIH4 0.0000E+00 0.0000E+00 7.0571E01 7.0571E01 Enthalpy (erg/g) 1.7981E+10 1.6033E+10 Internal Energy (erg/g) 1.6497E+10 1.4549E+10 Entropy (erg/g K) 7.6409E+07 7.6177E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 3.3333E01 9.3914E01 4.0059E02 1.1286E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 6.6667E01 6.0857E02 3.7339E01 3.4085E02 Volume (cm.sup.3/g) 1.6185E+03 1.6185E+03 SIH4 0.0000E+00 0.0000E+00 5.8655E01 8.5305E01 Enthalpy (erg/g) 1.8644E+10 1.6290E+10 Internal Energy (erg/g) 1.6487E+10 1.4132E+10 Entropy (erg/g K) 9.6982E+07 9.6988E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 2.5000E01 9.1141E01 1.8059E02 6.5837E02 Temperature (K) 5.7315E+02 5.7315E+02 H2 7.5000E01 8.8590E02 5.1806E01 6.1193E02 Volume (cm.sup.3/g) 2.0943E+03 2.0943E+03 SIH4 0.0000E+00 0.0000E+00 4.6388E01 8.7297E01 Enthalpy (erg/g) 1.9269E+10 1.6859E+10 Internal Energy (erg/g) 1.6477E+10 1.4067E+10 Entropy (erg/g K) 1.1612E+08 1.1647E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 2.0000E01 8.8527E01 1.0259E02 4.5412E02 Temperature (K) 5.7315E+02 5.7315E+02 H2 8.0000E01 1.1473E01 6.1026E01 8.7520E02 Volume (cm.sup.3/g) 2.5428E+03 2.5428E+03 SIH4 0.0000E+00 0.0000E+00 3.7948E01 8.6707E01 Enthalpy (erg/g) 1.9858E+10 1.7464E+10 Internal Energy (erg/g) 1.6467E+10 1.4074E+10 Entropy (erg/g K) 1.3405E+08 1.3467E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 1.6667E01 8.6058E01 6.6166E03 3.4165E02 Temperature (K) 5.7315E+02 5.7315E+02 H2 8.3333E01 1.3942E01 6.7328E01 1.1264E01 Volume (cm.sup.3/g) 2.9663E+03 2.9663E+03 SIH4 0.0000E+00 0.0000E+00 3.2010E01 8.5320E01 Enthalpy (erg/g) 2.0413E+10 1.8058E+10 Internal Energy (erg/g) 1.6459E+10 1.4104E+10 Entropy (erg/g K) 1.5093E+08 1.5175E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 1.4286E01 8.3724E01 4.6225E03 2.7091E02 Temperature (K) 5.7315E+02 5.7315E+02 H2 8.5714E01 1.6276E01 7.1891E01 1.3651E01 Volume (cm.sup.3/g) 3.3668E+03 3.3668E+03 SIH4 0.0000E+00 0.0000E+00 2.7647E01 8.3640E01 Enthalpy (erg/g) 2.0939E+10 1.8630E+10 Internal Energy (erg/g) 1.6450E+10 1.4142E+10 Entropy (erg/g K) 1.6685E+08 1.6784E+08

Example 3

Thermodynamic Equilibrium Calculation for the Hydrogenation of the Thermally Dissociated SiSi Bond

Generic Example: Si2H6 (g)+H2 (g)=>2 SiH4(g)

(77) Example 3 shows the effect of initial hydrogen content on the equilibrium concentration of hydrogenated monomer at P=1 atm and 1=200 C.

(78) TABLE-US-00003 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 4.0604E+01 SI2H6 1.0000E+00 1.0000E+00 1.1036E12 3.4056E11 Temperature (K) 4.7315E+02 4.7315E+02 H2 0.0000E+00 0.0000E+00 9.9999E01 9.9988E01 Volume (cm.sup.3/g) 4.7424E+02 4.7424E+02 SIH4 0.0000E+00 0.0000E+00 7.3056E06 1.1638E04 Enthalpy (erg/g) 1.5480E+10 2.5254E+10 Internal Energy (erg/g) 1.4848E+10 5.7430E+09 Entropy (erg/g K) 4.9914E+07 5.6160E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 8.3333E01 9.9356E01 6.6996E01 7.9878E01 Temperature (K) 4.7315E+02 4.7315E+02 H2 1.6667E01 6.4383E03 3.2949E03 1.2728E04 Volume (cm.sup.3/g) 5.6543E+02 5.6543E+02 SIH4 0.0000E+00 0.0000E+00 3.2674E01 2.0109E01 Enthalpy (erg/g) 1.5543E+10 1.5047E+10 Internal Energy (erg/g) 1.4789E+10 1.4293E+10 Entropy (erg/g K) 5.4837E+07 5.5120E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 7.1429E01 9.8721E01 4.4239E01 6.1142E01 Temperature (K) 4.7315E+02 4.7315E+02 H2 2.8571E01 1.2794E02 1.3821E02 6.1890E04 Volume (cm.sup.3/g) 6.5544E+02 6.5544E+02 SIH4 0.0000E+00 0.0000E+00 5.4379E01 3.8796E01 Enthalpy (erg/g) 1.5605E+10 1.4648E+10 Internal Energy (erg/g) 1.4731E+10 1.3774E+10 Entropy (erg/g K) 5.9376E+07 5.9582E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 6.2500E01 9.8093E01 2.8390E01 4.4557E01 Temperature (K) 4.7315E+02 4.7315E+02 H2 3.7500E01 1.9069E02 3.3897E02 1.7237E03 Volume (cm.sup.3/g) 7.4432E+02 7.4432E+02 SIH4 0.0000E+00 0.0000E+00 6.8221E01 5.5270E01 Enthalpy (erg/g) 1.5666E+10 1.4302E+10 Internal Energy (erg/g) 1.4674E+10 1.3310E+10 Entropy (erg/g K) 6.3757E+07 6.3799E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 5.5556E01 9.7473E01 1.7762E01 3.1164E01 Temperature (K) 4.7315E+02 4.7315E+02 H2 4.4444E01 2.5265E02 6.6509E02 3.7809E03 Volume (cm.sup.3/g) 8.3207E+02 8.3207E+02 SIH4 0.0000E+00 0.0000E+00 7.5587E01 6.8458E01 Enthalpy (erg/g) 1.5727E+10 1.4037E+10 Internal Energy (erg/g) 1.4618E+10 1.2928E+10 Entropy (erg/g K) 6.8027E+07 6.7921E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 5.0000E01 9.6862E01 1.1168E01 2.1634E01 Temperature (K) 4.7315E+02 4.7315E+02 H2 5.0000E01 3.1383E02 1.1168E01 7.0096E03 Volume (cm.sup.3/g) 9.1872E+02 9.1872E+02 SIH4 0.0000E+00 0.0000E+00 7.7665E01 7.7665E01 Enthalpy (erg/g) 1.5787E+10 1.3870E+10 Internal Energy (erg/g) 1.4562E+10 1.2645E+10 Entropy (erg/g K) 7.2207E+07 7.2036E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 3.3333E01 9.3914E01 2.2464E02 6.3292E02 Temperature (K) 4.7315E+02 4.7315E+02 H2 6.6667E01 6.0857E02 3.5580E01 3.2479E02 Volume (cm.sup.3/g) 1.3361E+03 1.3361E+03 SIH4 0.0000E+00 0.0000E+00 6.2174E01 9.0423E01 Enthalpy (erg/g) 1.6075E+10 1.3843E+10 Internal Energy (erg/g) 1.4293E+10 1.2062E+10 Entropy (erg/g K) 9.2060E+07 9.2305E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 2.5000E01 9.1141E01 9.3990E03 3.4265E02 Temperature (K) 4.7315E+02 4.7315E+02 H2 7.5000E01 8.8590E02 5.0940E01 6.0170E02 Volume (cm.sup.3/g) 1.7289E+03 1.7289E+03 SIH4 0.0000E+00 0.0000E+00 4.8120E01 9.0556E01 Enthalpy (erg/g) 1.6346E+10 1.4111E+10 Internal Energy (erg/g) 1.4041E+10 1.1806E+10 Entropy (erg/g K) 1.1052E+08 1.1120E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 2.0000E01 8.8527E01 5.1867E03 2.2958E02 Temperature (K) 4.7315E+02 4.7315E+02 H2 8.0000E01 1.1473E01 6.0519E01 8.6793E02 Volume (cm.sup.3/g) 2.0992E+03 2.0992E+03 SIH4 0.0000E+00 0.0000E+00 3.8963E01 8.9025E01 Enthalpy (erg/g) 1.6601E+10 1.4404E+10 Internal Energy (erg/g) 1.3803E+10 1.1606E+10 Entropy (erg/g K) 1.2781E+08 1.2881E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 1.6667E01 8.6058E01 3.2949E03 1.7013E02 Temperature (K) 4.7315E+02 4.7315E+02 H2 8.3333E01 1.3942E01 6.6996E01 1.1208E01 Volume (cm.sup.3/g) 2.4488E+03 2.4488E+03 SIH4 0.0000E+00 0.0000E+00 3.2674E01 8.7090E01 Enthalpy (erg/g) 1.6843E+10 1.4693E+10 Internal Energy (erg/g) 1.3578E+10 1.1429E+10 Entropy (erg/g K) 1.4408E+08 1.4531E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 1.4286E01 8.3724E01 2.2809E03 1.3368E02 Temperature (K) 4.7315E+02 4.7315E+02 H2 8.5714E01 1.6276E01 7.1657E01 1.3607E01 Volume (cm.sup.3/g) 2.7794E+03 2.7794E+03 SIH4 0.0000E+00 0.0000E+00 2.8115E01 8.5057E01 Enthalpy (erg/g) 1.7071E+10 1.4972E+10 Internal Energy (erg/g) 1.3365E+10 1.1267E+10 Entropy (erg/g K) 1.5944E+08 1.6083E+08

Example 4

Thermodynamic Equilibrium Calculation for the Hydrogenation of the Thermally Dissociated SiSi Bond

Generic Example: Si3H8 (g)+2H2 (g)=>3 SiH4(g)

(79) Example 4 shows the effect of initial hydrogen content on the equilibrium concentration of hydrogenated monomer at P=1 atm and T=200 C.

(80) TABLE-US-00004 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 6.0245E+01 SI3H8 1.0000E+00 1.0000E+00 3.9766E18 1.8208E16 Temperature (K) 4.7315E+02 4.7315E+02 H2 0.0000E+00 0.0000E+00 9.9999E01 9.9983E01 Volume (cm.sup.3/g) 3.1961E+02 3.1961E+02 SIH4 0.0000E+00 0.0000E+00 1.0839E05 1.7266E04 Enthalpy (erg/g) 1.5702E+10 2.5254E+10 Internal Energy (erg/g) 1.5276E+10 5.7434E+09 Entropy (erg/g K) 4.3522E+07 5.4530E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 8.3333E01 9.9565E01 7.5375E01 9.0057E01 Temperature (K) 4.7315E+02 4.7315E+02 H2 1.6667E01 4.3482E03 7.5078E03 1.9587E04 Volume (cm.sup.3/g) 3.8187E+02 3.8187E+02 SIH4 0.0000E+00 0.0000E+00 2.3874E01 9.9232E02 Enthalpy (erg/g) 1.5744E+10 1.5467E+10 Internal Energy (erg/g) 1.5235E+10 1.4958E+10 Entropy (erg/g K) 4.6875E+07 4.6937E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 7.1429E01 9.9134E01 5.8073E01 8.0598E01 Temperature (K) 4.7315E+02 4.7315E+02 H2 2.8571E01 8.6588E03 1.8597E02 5.6360E04 Volume (cm.sup.3/g) 4.4358E+02 4.4358E+02 SIH4 0.0000E+00 0.0000E+00 4.0068E01 1.9346E01 Enthalpy (erg/g) 1.5785E+10 1.5246E+10 Internal Energy (erg/g) 1.5193E+10 1.4655E+10 Entropy (erg/g K) 4.9981E+07 5.0003E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 6.2500E01 9.8707E01 4.5290E01 7.1527E01 Temperature (K) 4.7315E+02 4.7315E+02 H2 3.7500E01 1.2932E02 3.0803E02 1.0623E03 Volume (cm.sup.3/g) 5.0477E+02 5.0477E+02 SIH4 0.0000E+00 0.0000E+00 5.1630E01 2.8367E01 Enthalpy (erg/g) 1.5826E+10 1.5036E+10 Internal Energy (erg/g) 1.5153E+10 1.4363E+10 Entropy (erg/g K) 5.2992E+07 5.2943E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 5.5556E01 9.8283E01 3.5518E01 6.2835E01 Temperature (K) 4.7315E+02 4.7315E+02 H2 4.4444E01 1.7169E02 4.3698E02 1.6881E03 Volume (cm.sup.3/g) 5.6543E+02 5.6543E+02 SIH4 0.0000E+00 0.0000E+00 6.0112E01 3.6996E01 Enthalpy (erg/g) 1.5866E+10 1.4836E+10 Internal Energy (erg/g) 1.5112E+10 1.4083E+10 Entropy (erg/g K) 5.5940E+07 5.5803E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI2H6 5.0000E01 9.7863E01 2.7864E01 5.4538E01 Temperature (K) 4.7315E+02 4.7315E+02 H2 5.0000E01 2.1369E02 5.7286E02 2.4483E03 Volume (cm.sup.3/g) 6.2557E+02 6.2557E+02 SIH4 0.0000E+00 0.0000E+00 6.6407E01 4.5217E01 Enthalpy (erg/g) 1.5906E+10 1.4648E+10 Internal Energy (erg/g) 1.5072E+10 1.3814E+10 Entropy (erg/g K) 5.8838E+07 5.8603E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 3.3333E01 9.5816E01 7.2147E02 2.0738E01 Temperature (K) 4.7315E+02 4.7315E+02 H2 6.6667E01 4.1845E02 1.4429E01 9.0569E03 Volume (cm.sup.3/g) 9.1872E+02 9.1872E+02 SIH4 0.0000E+00 0.0000E+00 7.8356E01 7.8356E01 Enthalpy (erg/g) 1.6102E+10 1.3921E+10 Internal Energy (erg/g) 1.4877E+10 1.2696E+10 Entropy (erg/g K) 7.2769E+07 7.2122E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 2.5000E01 9.3852E01 1.4244E02 5.3473E02 Temperature (K) 4.7315E+02 4.7315E+02 H2 7.5000E01 6.1481E02 2.7849E01 2.2829E02 Volume (cm.sup.3/g) 1.1999E+03 1.1999E+03 SIH4 0.0000E+00 0.0000E+00 7.0727E01 9.2370E01 Enthalpy (erg/g) 1.6289E+10 1.3719E+10 Internal Energy (erg/g) 1.4690E+10 1.2119E+10 Entropy (erg/g K) 8.5973E+07 8.5474E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 2.0000E01 9.1967E01 3.8297E03 1.7610E02 Temperature (K) 4.7315E+02 4.7315E+02 H2 8.0000E01 8.0328E02 4.0766E01 4.0933E02 Volume (cm.sup.3/g) 1.4697E+03 1.4697E+03 SIH4 0.0000E+00 0.0000E+00 5.8851E01 9.4146E01 Enthalpy (erg/g) 1.6470E+10 1.3849E+10 Internal Energy (erg/g) 1.4510E+10 1.1890E+10 Entropy (erg/g K) 9.8575E+07 9.8547E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 1.6667E01 9.0157E01 1.5013E03 8.1212E03 Temperature (K) 4.7315E+02 4.7315E+02 H2 8.3333E01 9.8433E02 5.0300E01 5.9415E02 Volume (cm.sup.3/g) 1.7289E+03 1.7289E+03 SIH4 0.0000E+00 0.0000E+00 4.9550E01 9.3246E01 Enthalpy (erg/g) 1.6642E+10 1.4047E+10 Internal Energy (erg/g) 1.4337E+10 1.1742E+10 Entropy (erg/g K) 1.1064E+08 1.1103E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 1.4286E01 8.8416E01 7.3732E04 4.5634E03 Temperature (K) 4.7315E+02 4.7315E+02 H2 8.5714E01 1.1584E01 5.7290E01 7.7425E02 Volume (cm.sup.3/g) 1.9781E+03 1.9781E+03 SIH4 0.0000E+00 0.0000E+00 4.2636E01 9.1801E01 Enthalpy (erg/g) 1.6809E+10 1.4254E+10 Internal Energy (erg/g) 1.4171E+10 1.1617E+10 Entropy (erg/g K) 1.2221E+08 1.2293E+08

Example 5

Thermodynamic Equilibrium Calculation for the Hydrogenation of the Thermally Dissociated SiSi Bond

Generic Example: Si3H8 (g)+2H2 (g)=>3 SiH4(g)

(81) Example 5 shows the effect of initial hydrogen content on the equilibrium concentration of hydrogenated monomer at P=1 atm and T=300 C.

(82) TABLE-US-00005 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 6.0213E+01 SI3H8 1.0000E+00 1.0000E+00 1.0891E15 4.9843E14 Temperature (K) 5.7315E+02 5.7315E+02 H2 0.0000E+00 0.0000E+00 9.9995E01 9.9927E01 Volume (cm.sup.3/g) 3.8716E+02 3.8716E+02 SIH4 0.0000E+00 0.0000E+00 4.6101E05 7.3397E04 Enthalpy (erg/g) 1.7460E+10 3.9772E+10 Internal Energy (erg/g) 1.6944E+10 1.6151E+10 Entropy (erg/g K) 4.6887E+07 5.7291E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 8.3333E01 9.9565E01 7.5668E01 9.0407E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 1.6667E01 4.3482E03 1.3365E02 3.4868E04 Volume (cm.sup.3/g) 4.6258E+02 4.6258E+02 SIH4 0.0000E+00 0.0000E+00 2.2995E01 9.5581E02 Enthalpy (erg/g) 1.7557E+10 1.7254E+10 Internal Energy (erg/g) 1.6940E+10 1.6637E+10 Entropy (erg/g K) 5.0346E+07 5.0356E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 7.1429E01 9.9134E01 5.8755E01 8.1545E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 2.8571E01 8.6588E03 3.2245E02 9.7720E04 Volume (cm.sup.3/g) 5.3734E+02 5.3734E+02 SIH4 0.0000E+00 0.0000E+00 3.8020E01 1.8357E01 Enthalpy (erg/g) 1.7653E+10 1.7071E+10 Internal Energy (erg/g) 1.6937E+10 1.6354E+10 Entropy (erg/g K) 5.3558E+07 5.3495E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 6.2500E01 9.8707E01 4.6359E01 7.3215E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 3.7500E01 1.2932E02 5.2177E02 1.7994E03 Volume (cm.sup.3/g) 6.1145E+02 6.1145E+02 SIH4 0.0000E+00 0.0000E+00 4.8424E01 2.6605E01 Enthalpy (erg/g) 1.7749E+10 1.6904E+10 Internal Energy (erg/g) 1.6933E+10 1.6089E+10 Entropy (erg/g K) 5.6674E+07 5.6519E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 5.5556E01 9.8283E01 3.6950E01 6.5368E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 4.4444E01 1.7169E02 7.2328E02 2.7940E03 Volume (cm.sup.3/g) 6.8493E+02 6.8493E+02 SIH4 0.0000E+00 0.0000E+00 5.5817E01 3.4353E01 Enthalpy (erg/g) 1.7843E+10 1.6753E+10 Internal Energy (erg/g) 1.6930E+10 1.5840E+10 Entropy (erg/g K) 5.9726E+07 5.9471E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 5.0000E01 9.7863E01 2.9627E01 5.7988E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 5.0000E01 2.1369E02 9.2547E02 3.9554E03 Volume (cm.sup.3/g) 7.5778E+02 7.5778E+02 SIH4 0.0000E+00 0.0000E+00 6.1118E01 4.1616E01 Enthalpy (erg/g) 1.7937E+10 1.6616E+10 Internal Energy (erg/g) 1.6927E+10 1.5606E+10 Entropy (erg/g K) 6.2727E+07 6.2371E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 3.3333E01 9.5816E01 9.8883E02 2.8424E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 6.6667E01 4.1845E02 1.9777E01 1.2413E02 Volume (cm.sup.3/g) 1.1129E+03 1.1129E+03 SIH4 0.0000E+00 0.0000E+00 7.0335E01 7.0335E01 Enthalpy (erg/g) 1.8394E+10 1.6162E+10 Internal Energy (erg/g) 1.6910E+10 1.4679E+10 Entropy (erg/g K) 7.7159E+07 7.6411E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 2.5000E01 9.3852E01 3.1747E02 1.1918E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 7.5000E01 6.1481E02 3.1349E01 2.5698E02 Volume (cm.sup.3/g) 1.4534E+03 1.4534E+03 SIH4 0.0000E+00 0.0000E+00 6.5476E01 8.5512E01 Enthalpy (erg/g) 1.8833E+10 1.6119E+10 Internal Energy (erg/g) 1.6895E+10 1.4181E+10 Entropy (erg/g K) 9.0845E+07 9.0066E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 2.0000E01 9.1967E01 1.1293E02 5.1930E02 Temperature (K) 5.7315E+02 5.7315E+02 H2 8.0000E01 8.0328E02 4.2259E01 4.2432E02 Volume (cm.sup.3/g) 1.7803E+03 1.7803E+03 SIH4 0.0000E+00 0.0000E+00 5.6612E01 9.0564E01 Enthalpy (erg/g) 1.9254E+10 1.6380E+10 Internal Energy (erg/g) 1.6880E+10 1.4006E+10 Entropy (erg/g K) 1.0391E+08 1.0339E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 1.6667E01 9.0157E01 4.8895E03 2.6449E02 Temperature (K) 5.7315E+02 5.7315E+02 H2 8.3333E01 9.8433E02 5.0978E01 6.0215E02 Volume (cm.sup.3/g) 2.0943E+03 2.0943E+03 SIH4 0.0000E+00 0.0000E+00 4.8533E01 9.1334E01 Enthalpy (erg/g) 1.9658E+10 1.6760E+10 Internal Energy (erg/g) 1.6866E+10 1.3967E+10 Entropy (erg/g K) 1.1642E+08 1.1622E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 1.4286E01 8.8416E01 2.4976E03 1.5458E02 Temperature (K) 5.7315E+02 5.7315E+02 H2 8.5714E01 1.1584E01 5.7642E01 7.7901E02 Volume (cm.sup.3/g) 2.3962E+03 2.3962E+03 SIH4 0.0000E+00 0.0000E+00 4.2108E01 9.0664E01 Enthalpy (erg/g) 2.0047E+10 1.7169E+10 Internal Energy (erg/g) 1.6852E+10 1.3975E+10 Entropy (erg/g K) 1.2841E+08 1.2851E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 9.0909E02 8.2078E01 4.1945E04 3.7870E03 Temperature (K) 5.7315E+02 5.7315E+02 H2 9.0909E01 1.7922E01 7.2811E01 1.4355E01 Volume (cm.sup.3/g) 3.4955E+03 3.4955E+03 SIH4 0.0000E+00 0.0000E+00 2.7147E01 8.5267E01 Enthalpy (erg/g) 2.1462E+10 1.8756E+10 Internal Energy (erg/g) 1.6802E+10 1.4096E+10 Entropy (erg/g K) 1.7196E+08 1.7286E+08

Example 6

Thermodynamic Equilibrium Calculation for the Hydrogenation of the Thermally Dissociated SiSi Bond

Generic Example: Si3H8 (g)+2H2 (g)=>3 SiH4(g)

(83) Example 6 shows the effect of initial hydrogen content on the equilibrium concentration of hydrogenated monomer at P=1 atm and T=400 C.

(84) TABLE-US-00006 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 8.3333E01 9.9565E01 7.6024E01 9.0832E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 1.6667E01 4.3482E03 2.0478E02 5.3425E04 Volume (cm.sup.3/g) 5.4328E+02 5.4328E+02 SIH4 0.0000E+00 0.0000E+00 2.1928E01 9.1146E02 Enthalpy (erg/g) 1.9521E+10 1.9202E+10 Internal Energy (erg/g) 1.8797E+10 1.8478E+10 Entropy (erg/g K) 5.3502E+07 5.3487E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 7.1429E01 9.9134E01 5.9542E01 8.2637E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 2.8571E01 8.6588E03 4.7985E02 1.4542E03 Volume (cm.sup.3/g) 6.3109E+02 6.3109E+02 SIH4 0.0000E+00 0.0000E+00 3.5659E01 1.7217E01 Enthalpy (erg/g) 1.9672E+10 1.9070E+10 Internal Energy (erg/g) 1.8830E+10 1.8229E+10 Entropy (erg/g K) 5.6801E+07 5.6707E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 6.2500E01 9.8707E01 4.7541E01 7.5082E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 3.7500E01 1.2932E02 7.5816E02 2.6146E03 Volume (cm.sup.3/g) 7.1813E+02 7.1813E+02 SIH4 0.0000E+00 0.0000E+00 4.4878E01 2.4657E01 Enthalpy (erg/g) 1.9821E+10 1.8960E+10 Internal Energy (erg/g) 1.8864E+10 1.8002E+10 Entropy (erg/g K) 6.0005E+07 5.9821E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 5.5556E01 9.8283E01 3.8475E01 6.8065E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 4.4444E01 1.7169E02 1.0283E01 3.9722E03 Volume (cm.sup.3/g) 8.0443E+02 8.0443E+02 SIH4 0.0000E+00 0.0000E+00 5.1242E01 3.1537E01 Enthalpy (erg/g) 1.9970E+10 1.8868E+10 Internal Energy (erg/g) 1.8897E+10 1.7795E+10 Entropy (erg/g K) 6.3143E+07 6.2868E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 5.0000E01 9.7863E01 3.1441E01 6.1539E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 5.0000E01 2.1369E02 1.2883E01 5.5059E03 Volume (cm.sup.3/g) 8.8999E+02 8.8999E+02 SIH4 0.0000E+00 0.0000E+00 5.5676E01 3.7911E01 Enthalpy (erg/g) 2.0117E+10 1.8792E+10 Internal Energy (erg/g) 1.8930E+10 1.7606E+10 Entropy (erg/g K) 6.6229E+07 6.5865E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 3.3333E01 9.5816E01 1.2353E01 3.5507E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 6.6667E01 4.1845E02 2.4705E01 1.5507E02 Volume (cm.sup.3/g) 1.3071E+03 1.3071E+03 SIH4 0.0000E+00 0.0000E+00 6.2942E01 6.2942E01 Enthalpy (erg/g) 2.0833E+10 1.8634E+10 Internal Energy (erg/g) 1.9091E+10 1.6891E+10 Entropy (erg/g K) 8.1079E+07 8.0381E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 2.5000E01 9.3852E01 5.1389E02 1.9292E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 7.5000E01 6.1481E02 3.5278E01 2.8919E02 Volume (cm.sup.3/g) 1.7070E+03 1.7070E+03 SIH4 0.0000E+00 0.0000E+00 5.9583E01 7.7816E01 Enthalpy (erg/g) 2.1521E+10 1.8802E+10 Internal Energy (erg/g) 1.9245E+10 1.6526E+10 Entropy (erg/g K) 9.5165E+07 9.4375E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 2.0000E01 9.1967E01 2.2847E02 1.0506E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 8.0000E01 8.0328E02 4.4569E01 4.4752E02 Volume (cm.sup.3/g) 2.0909E+03 2.0909E+03 SIH4 0.0000E+00 0.0000E+00 5.3146E01 8.5019E01 Enthalpy (erg/g) 2.2180E+10 1.9210E+10 Internal Energy (erg/g) 1.9393E+10 1.6422E+10 Entropy (erg/g K) 1.0861E+08 1.0793E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 1.6667E01 9.0157E01 1.1231E02 6.0752E02 Temperature (K) 6.7315E+02 6.7315E+02 H2 8.3333E01 9.8433E02 5.2246E01 6.1713E02 Volume (cm.sup.3/g) 2.4597E+03 2.4597E+03 SIH4 0.0000E+00 0.0000E+00 4.6631E01 8.7753E01 Enthalpy (erg/g) 2.2814E+10 1.9748E+10 Internal Energy (erg/g) 1.9535E+10 1.6468E+10 Entropy (erg/g K) 1.2149E+08 1.2102E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 1.4286E01 8.8416E01 6.1253E03 3.7910E02 Temperature (K) 6.7315E+02 6.7315E+02 H2 8.5714E01 1.1584E01 5.8368E01 7.8882E02 Volume (cm.sup.3/g) 2.8143E+03 2.8143E+03 SIH4 0.0000E+00 0.0000E+00 4.1020E01 8.8321E01 Enthalpy (erg/g) 2.3423E+10 2.0337E+10 Internal Energy (erg/g) 1.9671E+10 1.6585E+10 Entropy (erg/g K) 1.3384E+08 1.3360E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 1.2500E01 8.6741E01 3.6489E03 2.5321E02 Temperature (K) 6.7315E+02 6.7315E+02 H2 8.7500E01 1.3259E01 6.3230E01 9.5810E02 Volume (cm.sup.3/g) 3.1554E+03 3.1554E+03 SIH4 0.0000E+00 0.0000E+00 3.6405E01 8.7887E01 Enthalpy (erg/g) 2.4010E+10 2.0938E+10 Internal Energy (erg/g) 1.9803E+10 1.6732E+10 Entropy (erg/g K) 1.4571E+08 1.4568E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SI3H8 9.0909E02 8.2078E01 1.1108E03 1.0029E02 Temperature (K) 6.7315E+02 6.7315E+02 H2 9.0909E01 1.7922E01 7.2949E01 1.4382E01 Volume (cm.sup.3/g) 4.1054E+03 4.1054E+03 SIH4 0.0000E+00 0.0000E+00 2.6939E01 8.4615E01 Enthalpy (erg/g) 2.5642E+10 2.2685E+10 Internal Energy (erg/g) 2.0169E+10 1.7212E+10 Entropy (erg/g K) 1.7868E+08 1.7918E+08

Example 7

Thermodynamic Equilibrium Calculation for the Hydrogenation of the Thermally Dissociated SiSi Bond

H3SiSiH2CH3(g)+2H2(g)=>SiH4(g)+H3SiCH3(g)

(85) Example 7 shows the effect of initial hydrogen content on the equilibrium concentration of hydrogenated monomer at P=1 atm and T=400 C.

(86) TABLE-US-00007 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 3.1589E+01 SIH3SIH2CH3 1.0000E+00 1.0000E+00 6.6350E07 1.5930E05 Temperature (K) 6.7315E+02 6.7315E+02 H2 0.0000E+00 0.0000E+00 9.7370E01 6.1809E01 Volume (cm.sup.3/g) 5.5058E+02 5.5058E+02 SIH4 0.0000E+00 0.0000E+00 6.4611E05 6.5344E04 Enthalpy (erg/g) 9.0048E+09 3.3931E+10 H3SICH3 0.0000E+00 0.0000E+00 2.6238E02 3.8124E01 Internal Energy (erg/g) 8.2708E+09 1.6308E+10 Entropy (erg/g K) 5.8826E+07 4.1364E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SIH3SIH2CH3 5.0000E01 9.7424E01 1.9085E01 3.7187E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 5.0000E01 2.5759E02 1.9085E01 9.8320E03 Volume (cm.sup.3/g) 1.0728E+03 1.0728E+03 SIH4 0.0000E+00 0.0000E+00 3.0915E01 2.5374E01 Enthalpy (erg/g) 1.0173E+10 8.5820E+09 H3SICH3 0.0000E+00 0.0000E+00 3.0915E01 3.6456E01 Internal Energy (erg/g) 8.7431E+09 7.1518E+09 Entropy (erg/g K) 7.8216E+07 7.7898E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SIH3SIH2CH3 3.3333E01 9.4978E01 6.7313E02 1.9180E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 6.6667E01 5.0223E02 4.0065E01 3.0183E02 Volume (cm.sup.3/g) 1.5688E+03 1.5688E+03 SIH4 0.0000E+00 0.0000E+00 2.6602E01 3.1929E01 Enthalpy (erg/g) 1.1283E+10 9.2808E+09 H3SICH3 0.0000E+00 0.0000E+00 2.6602E01 4.5873E01 Internal Energy (erg/g) 9.1917E+09 7.1893E+09 Entropy (erg/g K) 9.5738E+07 9.5475E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SIH3SIH2CH3 2.5000E01 9.2651E01 3.3487E02 1.2410E01 Temperature (K) 6.7315E+02 6.7315E+02 H2 7.5000E01 7.3490E02 5.3349E01 5.2274E02 Volume (cm.sup.3/g) 2.0405E+03 2.0405E+03 SIH4 0.0000E+00 0.0000E+00 2.1651E01 3.3800E01 Enthalpy (erg/g) 1.2339E+10 1.0219E+10 H3SICH3 0.0000E+00 0.0000E+00 2.1651E01 4.8562E01 Internal Energy (erg/g) 9.6184E+09 7.4987E+09 Entropy (erg/g K) 1.1222E+08 1.1213E+08

Example 8

Thermodynamic Equilibrium Calculation for the Hydrogenation of the Thermally Dissociated SiSi Bond

(H3SiSiH2CH3(g)+2H2(g)=>SiH4(g)+H3SiCH3(g)

(87) Example 8 shows the effect of initial hydrogen content on the equilibrium concentration of hydrogenated monomer at P=1 atm and T=300 C.

(88) TABLE-US-00008 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 2.5773E+01 SIH3SIH2CH3 1.0000E+00 1.0000E+00 1.6667E07 3.2648E06 Temperature (K) 5.7315E+02 5.7315E+02 H2 0.0000E+00 0.0000E+00 9.5747E01 4.9589E01 Volume (cm.sup.3/g) 4.6879E+02 4.6879E+02 SIH4 0.0000E+00 0.0000E+00 1.8091E05 1.4928E04 Enthalpy (erg/g) 6.9314E+09 1.8982E+10 H3SICH3 0.0000E+00 0.0000E+00 4.2510E02 5.0396E01 Internal Energy (erg/g) 6.3064E+09 6.7398E+09 Entropy (erg/g K) 5.5495E+07 3.3693E+08 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SIH3SIH2CH3 5.5556E01 9.7929E01 2.1873E01 3.8557E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 4.4444E01 2.0714E02 1.0762E01 5.0158E03 Volume (cm.sup.3/g) 8.2634E+02 8.2634E+02 SIH4 0.0000E+00 0.0000E+00 3.3682E01 2.5010E01 Enthalpy (erg/g) 7.6120E+09 6.1428E+09 H3SICH3 0.0000E+00 0.0000E+00 3.3682E01 3.5932E01 Internal Energy (erg/g) 6.5103E+09 5.0412E+09 Entropy (erg/g K) 7.0807E+07 7.0450E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SIH3SIH2CH3 5.0000E01 9.7424E01 1.5648E01 3.0490E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 5.0000E01 2.5759E02 1.5648E01 8.0614E03 Volume (cm.sup.3/g) 9.1342E+02 9.1342E+02 SIH4 0.0000E+00 0.0000E+00 3.4352E01 2.8195E01 Enthalpy (erg/g) 7.7778E+09 6.1215E+09 H3SICH3 0.0000E+00 0.0000E+00 3.4352E01 4.0509E01 Internal Energy (erg/g) 6.5599E+09 4.9038E+09 Entropy (erg/g K) 7.4367E+07 7.3945E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SIH3SIH2CH3 4.5455E01 9.6925E01 1.1553E01 2.4634E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 5.4545E01 3.0752E02 2.0644E01 1.1639E02 Volume (cm.sup.3/g) 9.9962E+02 9.9962E+02 SIH4 0.0000E+00 0.0000E+00 3.3902E01 3.0451E01 Enthalpy (erg/g) 7.9418E+09 6.1530E+09 H3SICH3 0.0000E+00 0.0000E+00 3.3902E01 4.3751E01 Internal Energy (erg/g) 6.6091E+09 4.8204E+09 Entropy (erg/g K) 7.7869E+07 7.7428E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SIH3SIH2CH3 3.3333E01 9.4978E01 4.5146E02 1.2940E01 Temperature (K) 5.7315E+02 5.7315E+02 H2 6.6667E01 5.0223E02 3.7875E01 2.8533E02 Volume (cm.sup.3/g) 1.3357E+03 1.3357E+03 SIH4 0.0000+00 0.0000+00 2.8792E01 3.4557E01 Enthalpy (erg/g) 8.5816E+09 6.5517E+09 H3SICH3 0.0000+00 0.0000+00 2.8792E01 4.9649E01 Internal Energy (erg/g) 6.8008E+09 1.7709E+09 Entropy (erg/g K) 9.1397E+07 9.1090E+07 Initial State Equilibrium State Initial Equilibrium mole mass mole mass State State fraction fraction fraction fraction Pressure (atm) 1.3158E+00 1.3157E+00 SIH3SIH2CH3 2.5000E01 9.2651E01 2.0907E02 7.7481E02 Temperature (K) 5.7315E+02 5.7315E+02 H2 7.5000E01 7.3490E02 5.2091E01 5.1042E02 Volume (cm.sup.3/g) 1.7373E+03 1.7673E+03 SIH4 0.0000E+00 0.0000E+00 2.2909E01 3.5764E01 Enthalpy (erg/g) 9.3461E+09 7.2452E+09 H3SICH3 0.0000E+00 0.0000E+00 2.2909E01 5.1384E01 Internal Energy (erg/g) 7.0298E+09 4.9291e+09 Entropy (erg/g K) 1.0741E+08 1.0735E+08

(89) While preferred embodiments have been described above and illustrated in the accompanying drawings, it will be evident to those skilled in the art that modifications may be made without departing from this disclosure. Such modifications are considered as possible variants comprised in the scope of the disclosure.