CA1178180A - Method for producing semiconductor grade silicon - Google Patents
Method for producing semiconductor grade siliconInfo
- Publication number
- CA1178180A CA1178180A CA000382630A CA382630A CA1178180A CA 1178180 A CA1178180 A CA 1178180A CA 000382630 A CA000382630 A CA 000382630A CA 382630 A CA382630 A CA 382630A CA 1178180 A CA1178180 A CA 1178180A
- Authority
- CA
- Canada
- Prior art keywords
- silicon
- silane
- halide
- hydrogen
- deposition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/025—Continuous growth
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/02—Silicon
- C01B33/021—Preparation
- C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
- C01B33/035—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition or reduction of gaseous or vaporised silicon compounds in the presence of heated filaments of silicon, carbon or a refractory metal, e.g. tantalum or tungsten, or in the presence of heated silicon rods on which the formed silicon is deposited, a silicon rod being obtained, e.g. Siemens process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45561—Gas plumbing upstream of the reaction chamber
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/14—Feed and outlet means for the gases; Modifying the flow of the reactive gases
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
Abstract
IMPROVED METHOD FOR PRODUCING
SEMICONDUCTOR GRADE SILICON
Abstract of the Disclosure An improved method of producing high purity silicon wherein the deposition rate for depositing silicon upon hot silicon carrier bodies through pyrolytic decomposition of silicon halide-hydrogen is significantly enhanced without increasing formation of free silicon particulate matter or silicon halide polymer coatings on reactor walls, the improvement resulting from the introduction of controlled amounts of less than 10% by weight of silane into the silicon halide-hydrogen reaction gas, the improved silicon deposition rate increasing substantially beyond the rate attributable to the stoichiometric addition amount of silane.
Inventor: Henry W. Gutsche
SEMICONDUCTOR GRADE SILICON
Abstract of the Disclosure An improved method of producing high purity silicon wherein the deposition rate for depositing silicon upon hot silicon carrier bodies through pyrolytic decomposition of silicon halide-hydrogen is significantly enhanced without increasing formation of free silicon particulate matter or silicon halide polymer coatings on reactor walls, the improvement resulting from the introduction of controlled amounts of less than 10% by weight of silane into the silicon halide-hydrogen reaction gas, the improved silicon deposition rate increasing substantially beyond the rate attributable to the stoichiometric addition amount of silane.
Inventor: Henry W. Gutsche
Description
~ ~ ~ 81~ O C19-21-0291A
IMPROVED METHOD FOR PRODUCING
SEMICONDUCTOR GRADE SILICON
Background of the Invention This invention relates to an improved process for growing silicon bodies resulting from chemical vapor deposition upon silicon carrier bodies. Another aspect of the invention relates to a process for improving the deposition rate of silicon upon sil con carrier bodies resulting from the addition of controlled amounts of silane to the silicon halide-hydrogen reaction gases which are then brought into contact with the hot silicon carrier bodies. In yet another aspect,the invention relates to a process for increasing the silicon deposition xate from silicon halide-hydrogen reaction gases within any chemical vapor deposition environment having the purpose of increasing the efficiency and deposition rate of silicon.
In the semiconductor industry, it is common to deposit material from the gaseous state onto a substrate for the purpose of forming various electronic devices.
In some applications the materia]. deposition of the gas is the same material as that from which the substrate is formed, while in other instances it is a di~ferent material from that from which th~ substrate is ~ormed.
As an example of the former, in t:he growth of silicon by vapor deposition techniques, it is common to position an elongated silicon filament between two graphite electrodes each of which extend through the end of a ~uartz container within which the filament is placed.
A potential is impressed across the graphite electrodes causing a current to flow through the ilament. ~he resistance of the filament produces a temperature generally in excess of about 1100C.
A gas stream, which comprises a mixture of tri-chlorosilane and hydrogen is introduced into the quartz l 1~ 81~ 0 C19-21-0291A
chamber and after flowing along the longitudinal axis of the fi.lament is withdrawn from the chamber. The gas stream, upon contacting the hot surface silicon filament, will react to deposit polycrystalline silicon on the fil-ament, thus increasing the diameter of the filament. Thereaction of the trichlorosilane and hydrogen may be generally illustrated by the following simplified formula:
Gas flow through the quartz cylinder or reaction chamber is usually continued for several hours to increase the diameter of the filament, which may be one-tenth inch in diameter upon commencement of the deposition, to the diameter in excess of five inches. When the silicon rod has reached a desired diameter, the flow is terminated and the rod is removed from the reaction chamber. M~terial deposited on the silicon filament will be polycrystalline and therefore must be zone melted to produce a single crystalline material. Alternatively, the poly crystal rod may be melted in a crucible and a large single rod is "pulled" from the melt by way of a variety of apparatus such as a Czochralski puller.
In both commercially accepted methods of producin~ single crystal silicon for the electronics industry, that is by float zone or by Czochralski, the single crystal rod which is drawn from a melt in both cases is rotated and results from the pulling of the melt in the form of the single crystal rod. Such methods require considerable skilled technician monitoring as well as multiple furnaces requiring substantial energy ~or operation. Even under the best conditions, frequently the crystal is iost during the first stage which means that the rod being pulled converts to a polysilicon growth zone; thus terminating the growth procedure of the rod.
Such commercial methods of producing remelt single crystal silicon rod materials are costly in time and effort and frequently produce irregularly shaped cylindri-cal rods requiring substantial premachining before slicing and conversion into wafers for use in the ~- electronics industry.
, ~ 17 8 ~ ~ ~ C19-21-0291A
In addition to the above commercial production means ~or producing electronic-grade semiconductor poly-crystalline, elemental silicon of electronic purity can be obtained~~by contacting a bed of silicon seed particles or carrier bodies at elevated tempera-tures with a hydrogen-stream containing a reduceable silicon compound such as silicon halide or a halosilane. Such process involves the charging of silicon seed particles''''~ ' through a suitable reactor wherein the seed particles are fluidized and maintained at temperatures ranging from about 1000C. to about 1250C. Hydrogen and tri-chlorosilane, for example, are passed through the bed at a rate sufficient to fluidize the seed particle bed while depositing additional elemental silicon thereon by hydrogen reduction of the trichlorosilane or other reducable silicon compound.
One advantage of such a process has been the feature of continuously or semi-continuously removing large silicon particles therefrom as a product of the process of concurrently adding seed particles to replenish the fluidized bed. A similar method for producing elemental silicon o~ electronic purity is ~ound in fluid wall reactor proce,sses wherein high energies are focused in a reaction zone with the reaction gases not being allowed to come in contact with the reactor walls. Such a process permits shifts to be made in the thermodynamics and kinetics of the silicon halide-hydrogen reaction process which heretofore was unattainable because of wall coating problems.
Whether using the older seed rod process or the more recent fluidized bed or fluid wall reactor, prior art processes have demonstrated the technical and economical feasibility of producing high-purity - polycrystalline silicon of semiconductor quality by l ~7~1~0 hydrogen reduction of silicon halides, All commercial semiconductor polycrystalline silicon presently being manufactured through chemical vapor deposition processes employ hydrogen reduction o~ trichlorosilane or silicon tetrachloride and the deposition of silicon on heated silicon carrier bodies.
Epitaxially-grown single crystal silicon by chemical vapor deposition (CVD) has been known since the early 1960's. It is also known to utilize the volatile exceptor or doner impurity precursors during growth process of silicon; thus leading to the formation of electrically-active regents, bounded by junc~ions of varying thicknesses, carrier concentrations, in junction profiles. Vapor substrate growth systems are quite general and in principle applicable to systems which are providing pertinent kinetic and thermodynamic conditi~ns of satisfactory balance.
The growth of single crystal silicon, for example, from the vapor phase i5 depended on several important paraMeters all of which interreact with each other to some degree. These parameters can be described in part, for example, as substrate surface crystalographic orientation, the chemical system, reaction variables, such as concentration, pressure, temperature modification, and the appropriate kinetic and thermodynamic ~actors. A variety of reaction systems have been investigated; however all have the common feature that a hot single crystal surface or a polycrystalline surface is exposed to an atmosphere which is thermally and/or chemically decomposable. The mechanism of the silicon-forming reaction is a function of the temperature of the substrate.
In the growth of polycrystalline silicon or single crystal silicon from deposition of silicon resulting from silicon halide-hydrogen reaction gases, the purity of the reaction gas is critical and is obtained by careful fractional distillation and by the particular design of the apparatus which assures that I ~ ~ 81~ Q C19-21-0291A
_5_ all materials used in the apparatus construction are very pure and do not promote contamination of the silicon halide-hydrogen reaction gases or depositing silicon under conditions of deposition. These requirements restrict the practical choice of materials that can be used for the construction of apparatus for the preparation of semiconduc~or silicon to quartz, graphite, silicon carbide, sllver, and the like. Silver must always be thoroughl~ water cooled in order to avoid chemical reaction.
The silicon halides used most for the preparation of high purity silicon are silicon tetrachloride and trichlorosilane. These halides will undergo pyrolysis when in contact with the hot surface and deposit elemental silicon. To obtain reasonable and economical yields, however, an excess of hydrogen gas is added to the silicon halides vapor reaction ~eed gas. Because of its higher silicon content, trichlorosilane will deposit more silicon than silicon tetrachloride and is therefore the preferred material for the Siemens' pro-cess for the preparation of polycrystalline silicon.However, silicon tetrachloride is preferred for the preparation of thin epitaxial films of single crystal silicon.
Silicon halides with less than three chlorine atoms in the molecule li~e SiH2C12 and SiH3Cl in particu~
lar, deposit much more silicon per mole of silicon halide consumed in the reaction but are impractical because they are not readily available and thus less desirable economically.
When trichlorosilane (SiHC13) or silicon tetrachloride ~SiC14) are used in the seed rod process/ -~
the overall reactions are assumed to be 1. SiHC13+H2-~Si + 3 HCl and
IMPROVED METHOD FOR PRODUCING
SEMICONDUCTOR GRADE SILICON
Background of the Invention This invention relates to an improved process for growing silicon bodies resulting from chemical vapor deposition upon silicon carrier bodies. Another aspect of the invention relates to a process for improving the deposition rate of silicon upon sil con carrier bodies resulting from the addition of controlled amounts of silane to the silicon halide-hydrogen reaction gases which are then brought into contact with the hot silicon carrier bodies. In yet another aspect,the invention relates to a process for increasing the silicon deposition xate from silicon halide-hydrogen reaction gases within any chemical vapor deposition environment having the purpose of increasing the efficiency and deposition rate of silicon.
In the semiconductor industry, it is common to deposit material from the gaseous state onto a substrate for the purpose of forming various electronic devices.
In some applications the materia]. deposition of the gas is the same material as that from which the substrate is formed, while in other instances it is a di~ferent material from that from which th~ substrate is ~ormed.
As an example of the former, in t:he growth of silicon by vapor deposition techniques, it is common to position an elongated silicon filament between two graphite electrodes each of which extend through the end of a ~uartz container within which the filament is placed.
A potential is impressed across the graphite electrodes causing a current to flow through the ilament. ~he resistance of the filament produces a temperature generally in excess of about 1100C.
A gas stream, which comprises a mixture of tri-chlorosilane and hydrogen is introduced into the quartz l 1~ 81~ 0 C19-21-0291A
chamber and after flowing along the longitudinal axis of the fi.lament is withdrawn from the chamber. The gas stream, upon contacting the hot surface silicon filament, will react to deposit polycrystalline silicon on the fil-ament, thus increasing the diameter of the filament. Thereaction of the trichlorosilane and hydrogen may be generally illustrated by the following simplified formula:
Gas flow through the quartz cylinder or reaction chamber is usually continued for several hours to increase the diameter of the filament, which may be one-tenth inch in diameter upon commencement of the deposition, to the diameter in excess of five inches. When the silicon rod has reached a desired diameter, the flow is terminated and the rod is removed from the reaction chamber. M~terial deposited on the silicon filament will be polycrystalline and therefore must be zone melted to produce a single crystalline material. Alternatively, the poly crystal rod may be melted in a crucible and a large single rod is "pulled" from the melt by way of a variety of apparatus such as a Czochralski puller.
In both commercially accepted methods of producin~ single crystal silicon for the electronics industry, that is by float zone or by Czochralski, the single crystal rod which is drawn from a melt in both cases is rotated and results from the pulling of the melt in the form of the single crystal rod. Such methods require considerable skilled technician monitoring as well as multiple furnaces requiring substantial energy ~or operation. Even under the best conditions, frequently the crystal is iost during the first stage which means that the rod being pulled converts to a polysilicon growth zone; thus terminating the growth procedure of the rod.
Such commercial methods of producing remelt single crystal silicon rod materials are costly in time and effort and frequently produce irregularly shaped cylindri-cal rods requiring substantial premachining before slicing and conversion into wafers for use in the ~- electronics industry.
, ~ 17 8 ~ ~ ~ C19-21-0291A
In addition to the above commercial production means ~or producing electronic-grade semiconductor poly-crystalline, elemental silicon of electronic purity can be obtained~~by contacting a bed of silicon seed particles or carrier bodies at elevated tempera-tures with a hydrogen-stream containing a reduceable silicon compound such as silicon halide or a halosilane. Such process involves the charging of silicon seed particles''''~ ' through a suitable reactor wherein the seed particles are fluidized and maintained at temperatures ranging from about 1000C. to about 1250C. Hydrogen and tri-chlorosilane, for example, are passed through the bed at a rate sufficient to fluidize the seed particle bed while depositing additional elemental silicon thereon by hydrogen reduction of the trichlorosilane or other reducable silicon compound.
One advantage of such a process has been the feature of continuously or semi-continuously removing large silicon particles therefrom as a product of the process of concurrently adding seed particles to replenish the fluidized bed. A similar method for producing elemental silicon o~ electronic purity is ~ound in fluid wall reactor proce,sses wherein high energies are focused in a reaction zone with the reaction gases not being allowed to come in contact with the reactor walls. Such a process permits shifts to be made in the thermodynamics and kinetics of the silicon halide-hydrogen reaction process which heretofore was unattainable because of wall coating problems.
Whether using the older seed rod process or the more recent fluidized bed or fluid wall reactor, prior art processes have demonstrated the technical and economical feasibility of producing high-purity - polycrystalline silicon of semiconductor quality by l ~7~1~0 hydrogen reduction of silicon halides, All commercial semiconductor polycrystalline silicon presently being manufactured through chemical vapor deposition processes employ hydrogen reduction o~ trichlorosilane or silicon tetrachloride and the deposition of silicon on heated silicon carrier bodies.
Epitaxially-grown single crystal silicon by chemical vapor deposition (CVD) has been known since the early 1960's. It is also known to utilize the volatile exceptor or doner impurity precursors during growth process of silicon; thus leading to the formation of electrically-active regents, bounded by junc~ions of varying thicknesses, carrier concentrations, in junction profiles. Vapor substrate growth systems are quite general and in principle applicable to systems which are providing pertinent kinetic and thermodynamic conditi~ns of satisfactory balance.
The growth of single crystal silicon, for example, from the vapor phase i5 depended on several important paraMeters all of which interreact with each other to some degree. These parameters can be described in part, for example, as substrate surface crystalographic orientation, the chemical system, reaction variables, such as concentration, pressure, temperature modification, and the appropriate kinetic and thermodynamic ~actors. A variety of reaction systems have been investigated; however all have the common feature that a hot single crystal surface or a polycrystalline surface is exposed to an atmosphere which is thermally and/or chemically decomposable. The mechanism of the silicon-forming reaction is a function of the temperature of the substrate.
In the growth of polycrystalline silicon or single crystal silicon from deposition of silicon resulting from silicon halide-hydrogen reaction gases, the purity of the reaction gas is critical and is obtained by careful fractional distillation and by the particular design of the apparatus which assures that I ~ ~ 81~ Q C19-21-0291A
_5_ all materials used in the apparatus construction are very pure and do not promote contamination of the silicon halide-hydrogen reaction gases or depositing silicon under conditions of deposition. These requirements restrict the practical choice of materials that can be used for the construction of apparatus for the preparation of semiconduc~or silicon to quartz, graphite, silicon carbide, sllver, and the like. Silver must always be thoroughl~ water cooled in order to avoid chemical reaction.
The silicon halides used most for the preparation of high purity silicon are silicon tetrachloride and trichlorosilane. These halides will undergo pyrolysis when in contact with the hot surface and deposit elemental silicon. To obtain reasonable and economical yields, however, an excess of hydrogen gas is added to the silicon halides vapor reaction ~eed gas. Because of its higher silicon content, trichlorosilane will deposit more silicon than silicon tetrachloride and is therefore the preferred material for the Siemens' pro-cess for the preparation of polycrystalline silicon.However, silicon tetrachloride is preferred for the preparation of thin epitaxial films of single crystal silicon.
Silicon halides with less than three chlorine atoms in the molecule li~e SiH2C12 and SiH3Cl in particu~
lar, deposit much more silicon per mole of silicon halide consumed in the reaction but are impractical because they are not readily available and thus less desirable economically.
When trichlorosilane (SiHC13) or silicon tetrachloride ~SiC14) are used in the seed rod process/ -~
the overall reactions are assumed to be 1. SiHC13+H2-~Si + 3 HCl and
2. SiC14 + 2 HCl-~Si + 4 HCl ~ ~7~80 C19-21~0291A
For a silicon halide to hydrogen mole ratio of 0.05%, thermal dynamic equilibrium is reached at 1150C.
when appro~imately 48~ of the SiC13 moles have reacted, or 24~ of the SiC1~ moles In practice, however, equilibrium is not reached in a flow-through system because the kinetics of the reaction limit the actual steady state silicon yields to about one-half of the equilibrium values, the hydrogen chloride desor~tion from the substrate surface being the rate controlling step in both reactions.
Any occurrence on the substrate surface that could accelerate the hydrogen chloride desorption movement of hydrogen chloride away from the surface would accelerate the deposition rate of silicon and improve~the economics of the process. One proven way to accomplish this result is to improve the deposition rate by accelerating the desorption rate of hydrogen chloride by raising the temperature of the substrate surface. This approach is effective but only when relatively small concentrations o~ silicon halide in the reaction gas are employed. These low mole ratios are lean mixtures and result in high yield but low weight gains. Rich mixtures do not respond in the desired manner because of side re!actions as Eollows:
SiHC13 -~(SiC12) + HCl and SiC14 + Si-~2 (SiC12); the side reaction producing the radical (SiC12) which is stable at the reaction temperature range and reduces the amount of reactive silicon halide available for absorption and reaction on the substrate surface. As a net effect, we see, in spite of the faster HC1 desorption, less silicon being deposited as we increase the substrate surface temperature from, for example, 1150C. to 1250C.
when molar ratios in excess of 0.05 in the trichlorosilane system and in excess of 0.01 molar ratio in the silicon tetrachloride system are utilized. In fact, at molar ratios of about 0.1 in the silicon tetrachloride system, the formation of (SiC12) becomes the dominant reaction and silicon is removed from the substrate at about 1200C.
Another approach to improved deposition rates would be to use mixtures of silicon halides so that the overall silicon chlorine ratios increase. For example, silane (SiH4) offers itself as an effective diluent and having no chlorine in the molecule would improve the silicon to chlorine ratios of silicon halide reaction gas mixtures. Silane as such cannot be used readily as a starting reaction material for the Siemens' process.
Silane is not stable and decomposes spontaneously at 400C. forming silicon and hydrogen. The silicon, unfortunately, forms a dust which is not suitable for further processing rather than a controlled deposition upon a seed rod. Only in greatly-diluted reaction gas stream whexein hydrogen, helium, or the li~e is utilized in the presence of hydrogen chloride, can silane be used to prepare silicon in crystalline form. Particular appli-cation is therefore limited mostly to slow deposition rateprocesses which are used exclusively in the thin film preparation field.
Summary of the Invention To overcome the ~ifficulties cited above, improved process according to the invention provides enhanced efficiency and deposition rate i~ comparing electronic grade silicon bodies from the deposition of silicon upon hot silicon carrier bodies. The method according to the in~Tention provides high-purity elemental silicon primarily for electronic semiconductor applications and in that respect is a significant improvement on the prior art methods. While for the purposes of this invention description, the processes described as relates to an improved silicon deposition process utilizing chemical vapor deposition technologies, the inventive l ~ 7 8 ~0 C19-21-029lA
process would enhance all silicon halide-hydrogen deposition systems.
The invention is predicated on the use of old and new apparatus refinements, thermodynamics and reaction kinetics wherein carrier bodies of crystalline silicon are exposed to silicon halide-hydrogen reaction gas mixtures at decomposition temperatures with the improvement being that the reaction gas is comprised of from about 0.2~ to less than 10% by weight silane in addition to the silicon halide-hydrogen feed stream. The introduction of small percentages by weight of silane to the silicon halide-hydrogen reaction gas, for example trichlorosilane and/or silicon tetrachloride produces increases in deposition rate which are beyond that attributable to the stoichiometric amounts of silane added to the reaction gas feed stream. A significant deposi~ion rate enhancement occurs through the utili~ation Of silane; thus the improvement according to the invention which is suitable for any electronic~grade silicon production wherein silicon halide-hydrogen reaction gases are thermally decomposed providing silicon for deposition growth upon ho-t silicon carrier bodies.
8rief Description of he Drawing The drawing which further elucidates the invention is a schematic and partially in-section presentation of an apparatus which is utilized in performing the novel improvement of the invention; the invention is not intended to be limited to this one simple drawing or apparatus representation since the addition of silane to a silicon halide-hydrogen pyrolytic system can utilize a variety of apparatus and methodology approaches.
Description of the Preferred Embodiments The invention provides a process for increasing silicon deposition rate from silicon halide-hydrogen . ~ . . . .. .
~ ~781~0 C19-21-0291A
_9_ gas systems which are capable pyrolytically depositing silicon on heated silicon carrier bodies under con-ditions which promote polycrystalline and in some cases single crystal silicon deposition. The process for S increasing the silicon deposition rate from silicon halide-hydrogen reaction gases wherein electronic-arade silicon bodies can be produced utilizing the step of introducing small percentages by weight oF
silane to the silicon halide-hydrogen reaction gases, for example, trichlorosilane and/or silicon tetrachloride.
A significant de~osition rate enhancement occurs through the utilization o~ controlled amounts of silane in combination with the silicon halide-hydrogen reaction gas feed. The thermodynamics of silicon halide-hydrogen systems are generally understood and the equilibrium compositions are fully quantified; however the kinetics o~ silicon vapor deposition (CVD) are not completely understood and multiple reactions appear to occur.
Quantitatively it is known that the deposition rate of silicon rises rapidly with temperature, then is less sensitive to temperature at higher temperatures, and may even drop with further increases in temperature within the upper limits. Mass trans~er and heat trans~er in silicon CV~ systems utilizing radiant heating have not previously been well understood and mostly continue to be evasive of exact quantification. Due to the complexity of the CVD process two specific goals were necessarily resolved through the invention, the enhanced direct silicon deposition rates while avoiding wall deposition or silicon dust.
The improved method according to the invention can be utilized in a variety of chemical pyrolytic decomposition systems wherein silicon is decomposed and deposits upon hot carrier bodies. However, behind this simple description, a number of complex phenomena remain ` l ~ 7 81~ ~ C19-21-0291A
for the most part unresolved. Chemical thermodynamics establish the maximum obtainable yields which depend on temperature and initial mole ratios. Various phase and gas solid reactions are involved, the kinetics of which depend on temperature, gas composition, and crystal orientation. Absorption-desorption of reaction end product on crys~al surfaces is also temperature dependent as are the rates in crystal growth nucleation. Finally, the gas composition and temperature on the crystal sur-face are affected by the flow pattern in the reactorwhich determines mass transportation transfer.
Before discussing the apparatus illustrated which represents only one of several methodologies suitable for the improvements offered by the present invention, it is noted that the main feature of the invention is to allow one to select specific deposition rates at optimum value and to maintain this value during the entire deposition process. In that regard, it is desirable to select a deposition ~te as large as possible, but in so doing to also insure that neither homogeneous nucleation of silicon in the feed gas phase nor deposition of silicon on the interior walls of the reactor walls occurs. In addition, the utilization of properly-prepared silicon carrier bodies creates the best possible d~posit.ion surface for creating single cry~tal or polycrystal sil.icon bodies. ~n apparatus which can be utilized in performance of the process according to the invention is schematically illustrated in the drawing; however the apparatus is representative of one of the many different types of apparatus useful for the performance of the inventive process.
In the figure, hydrogen to act as a reducing carrier gas is taken from hydrogen tank 1 through shut-off ~ ~ 7 8 1 8 ~ C19-21-0291A
valve 2 in a plural stage pressure reducing valve 3 and passes through a gas quantity meter 4 into a gas evaporator 5 where the hydrogen is mixed with the evaporation reaction gas such as silicon tetrachloride or trichlorosilane and silane. The silane is stored in tank 6 and flows through shut~off valve 7, pressure-reducing valve 8 and through gas quantity meter 9.
The mixture is passed through a gas supply pipe 10 and through a nozzle 11 into the processing space, the nozzle 11 producing a turbulent flow. The gas mixture passes along to carrier rods 13 of silicon which are electrically connected in series and during processing are transversed by alternating current supplied from an alternating current line in the terminals 12 for the purpose of heating the rods from about 1000C. to about 1300C., preferentially from about 1100C. to about 1250C. The carrier rods 13 are firmly attached to coaxial holders 15 of graphite and are sealed from the ~mbient atmosphere by means of a quartz cylinder 14.
The upper end of the rods 13 are interconnected by bridge 16 of silicon which forms a current-conducting connection between the rods. The! spent residual gases leave the processing space throuqh a heat insulated outlet pipe 17 and ~low along -the! gas inlet pipe in the direction opposed to that of the incoming gas mixture.
In the following examples, the invention is illustrated fully with experimental data where increased deposition rates of silicon from silicon halide-hydrogen process gas is achieved by adding silane in such a way to avoid dust formation but still permits a significant improvement in the deposition rate. In examples 1 and 2 following, commercial epitaxial reactor was utilized which allows heating of the silicon substrate wafer to about 1200C. and over and admittance of controlled amounts of silicon halide vapor and silane and hydrogen I :~78:~0 gas into -the reaction chamber. The substrate was placed in a rotating graphite susceptor. The susceptor was heated by an RF coil which was located beneath the susceptor and the gases were injected by means of a nozzle arrangement and impinged upon the substrate surface at a velocity of 15 meters per second. The results as indicated in examples 1 and 2 provide the realization that by adding silane to silicon tetrachloride or trichlorosilane, hydrogen process gas mixtures, an increase in deposition rates occur. The increase in deposition rates is larger than can be accounted for by silane weight addition alone. The increase in deposition rate was temperature dependent. This relationship has been used to calculate the activation energies of the respective reactions. Adding silane to a silicon halide process reaction gas reduces the activation energy of the silicon delivering reaction. The lower the substrate temperature, the more significant the improvement becomes. The results of the ollowing examples support the conclusion l:hat silane when added to silicon halide-hydrogen reaction gases in any process changes the silicon-chlorine ratLo on the substrate surface significantly more than :Ln the gas phase. The precise sur~ace reaction mechanism is not knownbut the lowering of the activation energy suggests "catalytic"
action and that the effect can be used to improve the economics of any pyrolytic silicon decomposition~
deposition process.
Example 1 Fifty milliliters per minute of silane were added to a process gas consisting of 1.3 liters of SiC14 ~apor plus 22.6 liters of hydrogen increasing the silicon content of the gas by only 3.8% by weight. The deposition rate of silicon was determined to increase from 1.87 microns per minute to 2.47 microns per minute or a 32~ enhancement I ~ 781~0 C19-21-0291A
in deposition rate resulting from the silane addition.
The temperature was 1125C. When the substrate surface temperatures were brought up to 1150C., the deposition rate rose ~rom 3.33 microns per minute to 4.1 microns per minute for 23~ increase in deposition rate resulting from the silane added reaction gas mixture. These rates were measured on (110) silicon planes.
Example 2 Silicon substrates having (112) orientation were utilized in the same reactor conditions as described in example 1, with the following deposition rate increases measured at 1125C. The deposition rate utilizing the silicon halide-hydrogen reactor gas ~eed stream was 1.74 microns per minute whereas the reactor gas feed stream utilizing silane pushed the deposition rate to 2.41 microns per minute resulting in a 39% deposition rate. When repeating the experiment at 1200C., the rate rose ~rom 4.55 microns per minute to 5.26 micro~s per minute resulting in a 16~ deposition rate increase through the utilization of silane in combination with silicon halide-hydrogen reactor gas systems.
The experimental results as illustrated in examples 1 and 2 clearly tsach that the addition o~
silane is bene~icial ~or the deposition o~ elemental silicon from silicon halide-hydrogen reaction gas mixtures because it increases the deposition rate signi~icantly beyond what is expected.
. .
For a silicon halide to hydrogen mole ratio of 0.05%, thermal dynamic equilibrium is reached at 1150C.
when appro~imately 48~ of the SiC13 moles have reacted, or 24~ of the SiC1~ moles In practice, however, equilibrium is not reached in a flow-through system because the kinetics of the reaction limit the actual steady state silicon yields to about one-half of the equilibrium values, the hydrogen chloride desor~tion from the substrate surface being the rate controlling step in both reactions.
Any occurrence on the substrate surface that could accelerate the hydrogen chloride desorption movement of hydrogen chloride away from the surface would accelerate the deposition rate of silicon and improve~the economics of the process. One proven way to accomplish this result is to improve the deposition rate by accelerating the desorption rate of hydrogen chloride by raising the temperature of the substrate surface. This approach is effective but only when relatively small concentrations o~ silicon halide in the reaction gas are employed. These low mole ratios are lean mixtures and result in high yield but low weight gains. Rich mixtures do not respond in the desired manner because of side re!actions as Eollows:
SiHC13 -~(SiC12) + HCl and SiC14 + Si-~2 (SiC12); the side reaction producing the radical (SiC12) which is stable at the reaction temperature range and reduces the amount of reactive silicon halide available for absorption and reaction on the substrate surface. As a net effect, we see, in spite of the faster HC1 desorption, less silicon being deposited as we increase the substrate surface temperature from, for example, 1150C. to 1250C.
when molar ratios in excess of 0.05 in the trichlorosilane system and in excess of 0.01 molar ratio in the silicon tetrachloride system are utilized. In fact, at molar ratios of about 0.1 in the silicon tetrachloride system, the formation of (SiC12) becomes the dominant reaction and silicon is removed from the substrate at about 1200C.
Another approach to improved deposition rates would be to use mixtures of silicon halides so that the overall silicon chlorine ratios increase. For example, silane (SiH4) offers itself as an effective diluent and having no chlorine in the molecule would improve the silicon to chlorine ratios of silicon halide reaction gas mixtures. Silane as such cannot be used readily as a starting reaction material for the Siemens' process.
Silane is not stable and decomposes spontaneously at 400C. forming silicon and hydrogen. The silicon, unfortunately, forms a dust which is not suitable for further processing rather than a controlled deposition upon a seed rod. Only in greatly-diluted reaction gas stream whexein hydrogen, helium, or the li~e is utilized in the presence of hydrogen chloride, can silane be used to prepare silicon in crystalline form. Particular appli-cation is therefore limited mostly to slow deposition rateprocesses which are used exclusively in the thin film preparation field.
Summary of the Invention To overcome the ~ifficulties cited above, improved process according to the invention provides enhanced efficiency and deposition rate i~ comparing electronic grade silicon bodies from the deposition of silicon upon hot silicon carrier bodies. The method according to the in~Tention provides high-purity elemental silicon primarily for electronic semiconductor applications and in that respect is a significant improvement on the prior art methods. While for the purposes of this invention description, the processes described as relates to an improved silicon deposition process utilizing chemical vapor deposition technologies, the inventive l ~ 7 8 ~0 C19-21-029lA
process would enhance all silicon halide-hydrogen deposition systems.
The invention is predicated on the use of old and new apparatus refinements, thermodynamics and reaction kinetics wherein carrier bodies of crystalline silicon are exposed to silicon halide-hydrogen reaction gas mixtures at decomposition temperatures with the improvement being that the reaction gas is comprised of from about 0.2~ to less than 10% by weight silane in addition to the silicon halide-hydrogen feed stream. The introduction of small percentages by weight of silane to the silicon halide-hydrogen reaction gas, for example trichlorosilane and/or silicon tetrachloride produces increases in deposition rate which are beyond that attributable to the stoichiometric amounts of silane added to the reaction gas feed stream. A significant deposi~ion rate enhancement occurs through the utili~ation Of silane; thus the improvement according to the invention which is suitable for any electronic~grade silicon production wherein silicon halide-hydrogen reaction gases are thermally decomposed providing silicon for deposition growth upon ho-t silicon carrier bodies.
8rief Description of he Drawing The drawing which further elucidates the invention is a schematic and partially in-section presentation of an apparatus which is utilized in performing the novel improvement of the invention; the invention is not intended to be limited to this one simple drawing or apparatus representation since the addition of silane to a silicon halide-hydrogen pyrolytic system can utilize a variety of apparatus and methodology approaches.
Description of the Preferred Embodiments The invention provides a process for increasing silicon deposition rate from silicon halide-hydrogen . ~ . . . .. .
~ ~781~0 C19-21-0291A
_9_ gas systems which are capable pyrolytically depositing silicon on heated silicon carrier bodies under con-ditions which promote polycrystalline and in some cases single crystal silicon deposition. The process for S increasing the silicon deposition rate from silicon halide-hydrogen reaction gases wherein electronic-arade silicon bodies can be produced utilizing the step of introducing small percentages by weight oF
silane to the silicon halide-hydrogen reaction gases, for example, trichlorosilane and/or silicon tetrachloride.
A significant de~osition rate enhancement occurs through the utilization o~ controlled amounts of silane in combination with the silicon halide-hydrogen reaction gas feed. The thermodynamics of silicon halide-hydrogen systems are generally understood and the equilibrium compositions are fully quantified; however the kinetics o~ silicon vapor deposition (CVD) are not completely understood and multiple reactions appear to occur.
Quantitatively it is known that the deposition rate of silicon rises rapidly with temperature, then is less sensitive to temperature at higher temperatures, and may even drop with further increases in temperature within the upper limits. Mass trans~er and heat trans~er in silicon CV~ systems utilizing radiant heating have not previously been well understood and mostly continue to be evasive of exact quantification. Due to the complexity of the CVD process two specific goals were necessarily resolved through the invention, the enhanced direct silicon deposition rates while avoiding wall deposition or silicon dust.
The improved method according to the invention can be utilized in a variety of chemical pyrolytic decomposition systems wherein silicon is decomposed and deposits upon hot carrier bodies. However, behind this simple description, a number of complex phenomena remain ` l ~ 7 81~ ~ C19-21-0291A
for the most part unresolved. Chemical thermodynamics establish the maximum obtainable yields which depend on temperature and initial mole ratios. Various phase and gas solid reactions are involved, the kinetics of which depend on temperature, gas composition, and crystal orientation. Absorption-desorption of reaction end product on crys~al surfaces is also temperature dependent as are the rates in crystal growth nucleation. Finally, the gas composition and temperature on the crystal sur-face are affected by the flow pattern in the reactorwhich determines mass transportation transfer.
Before discussing the apparatus illustrated which represents only one of several methodologies suitable for the improvements offered by the present invention, it is noted that the main feature of the invention is to allow one to select specific deposition rates at optimum value and to maintain this value during the entire deposition process. In that regard, it is desirable to select a deposition ~te as large as possible, but in so doing to also insure that neither homogeneous nucleation of silicon in the feed gas phase nor deposition of silicon on the interior walls of the reactor walls occurs. In addition, the utilization of properly-prepared silicon carrier bodies creates the best possible d~posit.ion surface for creating single cry~tal or polycrystal sil.icon bodies. ~n apparatus which can be utilized in performance of the process according to the invention is schematically illustrated in the drawing; however the apparatus is representative of one of the many different types of apparatus useful for the performance of the inventive process.
In the figure, hydrogen to act as a reducing carrier gas is taken from hydrogen tank 1 through shut-off ~ ~ 7 8 1 8 ~ C19-21-0291A
valve 2 in a plural stage pressure reducing valve 3 and passes through a gas quantity meter 4 into a gas evaporator 5 where the hydrogen is mixed with the evaporation reaction gas such as silicon tetrachloride or trichlorosilane and silane. The silane is stored in tank 6 and flows through shut~off valve 7, pressure-reducing valve 8 and through gas quantity meter 9.
The mixture is passed through a gas supply pipe 10 and through a nozzle 11 into the processing space, the nozzle 11 producing a turbulent flow. The gas mixture passes along to carrier rods 13 of silicon which are electrically connected in series and during processing are transversed by alternating current supplied from an alternating current line in the terminals 12 for the purpose of heating the rods from about 1000C. to about 1300C., preferentially from about 1100C. to about 1250C. The carrier rods 13 are firmly attached to coaxial holders 15 of graphite and are sealed from the ~mbient atmosphere by means of a quartz cylinder 14.
The upper end of the rods 13 are interconnected by bridge 16 of silicon which forms a current-conducting connection between the rods. The! spent residual gases leave the processing space throuqh a heat insulated outlet pipe 17 and ~low along -the! gas inlet pipe in the direction opposed to that of the incoming gas mixture.
In the following examples, the invention is illustrated fully with experimental data where increased deposition rates of silicon from silicon halide-hydrogen process gas is achieved by adding silane in such a way to avoid dust formation but still permits a significant improvement in the deposition rate. In examples 1 and 2 following, commercial epitaxial reactor was utilized which allows heating of the silicon substrate wafer to about 1200C. and over and admittance of controlled amounts of silicon halide vapor and silane and hydrogen I :~78:~0 gas into -the reaction chamber. The substrate was placed in a rotating graphite susceptor. The susceptor was heated by an RF coil which was located beneath the susceptor and the gases were injected by means of a nozzle arrangement and impinged upon the substrate surface at a velocity of 15 meters per second. The results as indicated in examples 1 and 2 provide the realization that by adding silane to silicon tetrachloride or trichlorosilane, hydrogen process gas mixtures, an increase in deposition rates occur. The increase in deposition rates is larger than can be accounted for by silane weight addition alone. The increase in deposition rate was temperature dependent. This relationship has been used to calculate the activation energies of the respective reactions. Adding silane to a silicon halide process reaction gas reduces the activation energy of the silicon delivering reaction. The lower the substrate temperature, the more significant the improvement becomes. The results of the ollowing examples support the conclusion l:hat silane when added to silicon halide-hydrogen reaction gases in any process changes the silicon-chlorine ratLo on the substrate surface significantly more than :Ln the gas phase. The precise sur~ace reaction mechanism is not knownbut the lowering of the activation energy suggests "catalytic"
action and that the effect can be used to improve the economics of any pyrolytic silicon decomposition~
deposition process.
Example 1 Fifty milliliters per minute of silane were added to a process gas consisting of 1.3 liters of SiC14 ~apor plus 22.6 liters of hydrogen increasing the silicon content of the gas by only 3.8% by weight. The deposition rate of silicon was determined to increase from 1.87 microns per minute to 2.47 microns per minute or a 32~ enhancement I ~ 781~0 C19-21-0291A
in deposition rate resulting from the silane addition.
The temperature was 1125C. When the substrate surface temperatures were brought up to 1150C., the deposition rate rose ~rom 3.33 microns per minute to 4.1 microns per minute for 23~ increase in deposition rate resulting from the silane added reaction gas mixture. These rates were measured on (110) silicon planes.
Example 2 Silicon substrates having (112) orientation were utilized in the same reactor conditions as described in example 1, with the following deposition rate increases measured at 1125C. The deposition rate utilizing the silicon halide-hydrogen reactor gas ~eed stream was 1.74 microns per minute whereas the reactor gas feed stream utilizing silane pushed the deposition rate to 2.41 microns per minute resulting in a 39% deposition rate. When repeating the experiment at 1200C., the rate rose ~rom 4.55 microns per minute to 5.26 micro~s per minute resulting in a 16~ deposition rate increase through the utilization of silane in combination with silicon halide-hydrogen reactor gas systems.
The experimental results as illustrated in examples 1 and 2 clearly tsach that the addition o~
silane is bene~icial ~or the deposition o~ elemental silicon from silicon halide-hydrogen reaction gas mixtures because it increases the deposition rate signi~icantly beyond what is expected.
. .
Claims (7)
1. In a method of producing silicon or high purity suitable for semiconductor use, wherein silicon is deposited onto hot silicon carrier bodies at temper-atures of from about 1000°C. to about 1300°C. through pyrolytic decomposition of silicon halide-hydrogen reaction gases which are placed in contact with the hot silicon bodies, the improvement comprising:
contacting the heated silicon bodies with silicon halide-hydrogen reaction gases containing from about 0.2% to about 5% by weight silane;
increasing the silicon deposition rate as a result of the silane addition, said increase being in greater magnitude than the stoichiometric relationship of the added silane content; and maintaining minimum formation of free silicon particulate matter or silicon halide polymer coating on reactor walls.
contacting the heated silicon bodies with silicon halide-hydrogen reaction gases containing from about 0.2% to about 5% by weight silane;
increasing the silicon deposition rate as a result of the silane addition, said increase being in greater magnitude than the stoichiometric relationship of the added silane content; and maintaining minimum formation of free silicon particulate matter or silicon halide polymer coating on reactor walls.
2. The method according to claim 1 wherein a sili-con halide-hydrogen reaction gas is comprised of trichlorosilane.
3. The method according to claim 1 where the deposition rate for the silicon deposition is of a magnitude of at least three fold greater than the rate increase attributable to the stoichiometric amount of silane added.
4. The method according to claim 1 wherein silicon is deposited upon hot carrier rod silicon bodies within an at least partially transparent reaction vessel at least partially comprised of material taken from the group consisting with glass and quartz, said vessel being in the general shape of a bell jar.
5. The method according to claim 1 wherein the improved deposition rate of silicon is achieved through the controlled silane addition to the silicon halogen-hydrogen reactor gas in a fluidized bed environment wherein multiple silicon carrier bodies are contacted with the reaction gas in the fluidized bed.
6. In the method according to claim 1 wherein the silicon halide-hydrogen reaction gas including the controlled amounts of silane are contacted with multiple silicon carrier bodies within a fluid wall reactor.
7. The method according to claim 1 wherein the silicon halide-hydrogen reaction gases containing controlled amounts of silane brought into contact with the silicon carrier body having the configuration of a ribbon, said ribbon being enclosed in a quartz or glass bell jar-type reactor.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17262580A | 1980-07-28 | 1980-07-28 | |
| US172,625 | 1980-07-28 |
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| Publication Number | Publication Date |
|---|---|
| CA1178180A true CA1178180A (en) | 1984-11-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000382630A Expired CA1178180A (en) | 1980-07-28 | 1981-07-27 | Method for producing semiconductor grade silicon |
Country Status (3)
| Country | Link |
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| JP (1) | JPS5751114A (en) |
| KR (1) | KR850001945B1 (en) |
| CA (1) | CA1178180A (en) |
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1981
- 1981-07-27 CA CA000382630A patent/CA1178180A/en not_active Expired
- 1981-07-27 JP JP56117567A patent/JPS5751114A/en active Pending
- 1981-07-27 KR KR1019810002713A patent/KR850001945B1/en active IP Right Grant
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| Publication number | Publication date |
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| JPS5751114A (en) | 1982-03-25 |
| KR850001945B1 (en) | 1985-12-31 |
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