US3239372A - Method of producing single crystal silicon - Google Patents

Method of producing single crystal silicon Download PDF

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Publication number
US3239372A
US3239372A US81607A US8160761A US3239372A US 3239372 A US3239372 A US 3239372A US 81607 A US81607 A US 81607A US 8160761 A US8160761 A US 8160761A US 3239372 A US3239372 A US 3239372A
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silicon
temperature
reaction gas
separation
carrier
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Expired - Lifetime
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US81607A
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English (en)
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Sirtl Erhard
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Siemens and Halske AG
Siemens AG
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Siemens AG
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Priority claimed from DES66651A external-priority patent/DE1124028B/de
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    • 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
    • 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
    • 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
    • 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

Definitions

  • the prior application describes a method of producing highly pure silicon, utilizing a reaction gas consisting of a purified halogen-containing silicon compound which is preferably intermixed with purified hydrogen, such reaction gas being caused to flow along a carrier body made of hyperpure silicon, which is disposed in a reaction vessel and heated by direct current passage therethrough, thereby causing precipitation upon the carrier body of silicon liberated or separated from the reaction gas by thermal decomposition and crystallization thereon to effect growth of the carrier body.
  • the prior application proposes to use as a carrier a thin elongated silicon rod, especially a silicon wire which is held in the reaction vessel by means of electrodes engaging its ends, and is after preheating thereof caused to glow by the action of electric current conducted thereto over the electrodes.
  • the reaction gas flowing along the hot carrier decomposes due to the heat given off therefrom, liberates or separates silicon which is precipitated upon the carrier and caused to crystallize thereon.
  • the crystal structure of the precipitated silicon is codetermined by the crystal structure of the carrier. Accordingly, there is in principle the possibility of effecting single crystal decomposition by using a monocrystalline carrier.
  • the method described in such prior application proposes to heat the surface structure of a monocrystalline carrier body, which had been exposed, for example, by etching, to a temperature lying below the temperature at which is effected the maximum precipitation upon the semiconductor body of the semiconductor substance at the reaction utilized therefor, also, to cause the reaction gas to flow turbulently about the surface of the carrier body and further, to adjust in known manner the decomposition velocity effected at the applied working temperature and reaction, so as to avoid 3,2393 Patented Mar. 8, 1966 oversaturation of the carrier body with the liberated semiconductor material.
  • the present invention is concerned with a method of producing single crystal silicon, wherein a flowing reaction gas consisting of a halogen-containing silicon compound, especially halogen silane, preferably intermixed with purified hydrogen, is conducted along an electrically heated single crystal carrier body of pure or doped silicon, which is held in a reaction vessel, to elfect precipitation of silicon, separated from the reaction gas respectively by thermal and electrothermal conversion or decomposition, upon the carrier and monocrystalline growth thereof on such carrier.
  • a flowing reaction gas consisting of a halogen-containing silicon compound, especially halogen silane, preferably intermixed with purified hydrogen
  • a halogen compound which is also formed in the reaction gas during the decomposition process, preferably a hydrogen halide, which shifts the reaction equilibrium in favor of the bound silicon, in an amount such that the temperature T of the chemical equilibrium (that is, the temperature at which there is neither silicon separation nor recharging of silicon already present) of the substances which are present in the reaction gas and partake in the separation reaction, lies at the most 200 C. below the applied separation temperature T, and that the silicon separation is completely interrupted below the equilibrium temperature T
  • the equilibrium temperature shall advantageously not lie below 900 C.
  • the thermal conversion or electrothermal conversion (that is, effected by an electrical gas discharge) of the reaction gas will as a rule produce, owing to the use, in accordance with the teaching of the invention, of a halogen-containing silicon compound, new halogen-containing compounds which are absent in the initial reaction gas and which upon customary application of a flowing reaction gas generally escape from the reaction vessel with the waste gases.
  • Hydrogen halide substances will primarily appear when using a halogen silane as an initial compound and intermixing therewith a gaseous reduction agent, in practice purified hydrogen, for the purpose of increasing to an economically justifiable amount separation at a temperature lying below the melting point of silicon.
  • the invention proposes, for these reasons, to conduct to the reaction gas primarily a hydrogen compound of the halogen element which is also bound in the silicon compound of the reaction gas that is being used.
  • FIGS. 1 and 2 show curves representing amounts of silicon separated from the reaction gas depending upon the surface temperature of the carrier body
  • FIG. 3 shows an example of the apparatus for practicing the invention.
  • the curves a, b and c, FIG. 1 were obtained with a reaction mixture of 95 mole percent of hydrogen and mole percent of SiCl (no) (n as used herein, referring to molar concentration employing SiCl concentration as the base), which was conducted through the separation apparatus in steady flow.
  • the curve b was obtained responsive to adding to this reaction mixture 1.5 mole percent HCl (0.312 and the curve 0 was obtained upon adding thereto mole percent HQ (312
  • the carrier is electrically heated. Whether. inductive heating is applied or energy is supplied to the ends of the carrier over-the electrodes connected therewith, those parts which project from the carrier surface will have the lowest temperature, while recessed areas will be hottest. Accordingly, the protruding parts, for example,'wart-like protuberances and the like should responsive to electrical overheating receive less separated material than the recessed parts, for example, grooves or pockets.
  • the separation curve defines a definite intersection point T with the temperature axis.
  • the separation curve is moreover so adjusted that even slight temperature increases above T result in a relatively greatyield.
  • the Working temperature T of the carrier surface is such that the protruding, that is, the relatively cold parts, receive little separated material until they are evened up and their temperature is approximated ,to the desired valueT.
  • FIG. 3 shows by way of example an arrangement for carrying out the method according to the invention.
  • Numeral 1 indicates a quartz vessel in which 'is'dis posed a thin rod 2 consisting of 'hyperpure or doped silicon upon which is to be precipitated respectively byperpure or doped silicon obtained from a gaseous phase so as to grow thereon in monocrystalline manner.
  • Electrodes 3 and 3" made of heat resistant material such as graphite,.molybdenum and the like, which shall be as pure as possible, serve for holding the rod 2 in place;
  • the rod 2 is held at the separation temperature T, for example, 1150 -C., by electric current 'passingtherethrough, which is supplied from a current source 5 over an adjustable stabilizing resistor .4.
  • a vaporizing vessel 8 made of quartz, is provided for producing the reaction gas, such vessel containing SiCl or SiHCl in liquid condition.
  • a receptacle 9 which contains highly pure distilled water which drops in regulatable manner into the SiCl or SiHCl contained in the vessel 8.
  • Some of the silicon halide compound contained in the vaporizaton vessel is thereby hydrolized, thereby producing HCl and silicic acid.
  • Highly purified hydrogen is supplied to the vaporizer 8 at 10 in a regulatable stream and is loaded with the abundantly present vapor of the silicon compound and with the developed HCl, whereupon it is conducted, if desired with further addition of hydrogen, over a cooling trap 12 (for freezing out the water vapors) into the separation vessel 1.
  • a further vaporization vessel supplied with SiCl or SiHCl can be connected serially with or in parallel with the vaporizer 8, which distinguishes from 8 in that no HCl is developed therein.
  • the vaporizer or Vaporizers are respectively arranged in a temperature bath 11 which is utilized for regulating the rate of vaporization of the silicon compound.
  • the adjustment of the temperature in the vaporizer as well as of the velocity of the hydrogen stream and the amount of distilled water-supplied in drops from the receptacle 9, give the possibility of regulating the composition of the reaction gasin desired and definite manner.
  • the separation curve is by the content of HCl shifted in the described manner so as to fulfill, in cooperation with the surface temperature T of the carrier, the teachings of the invention.
  • the waste gas discharged from a like or similar separation apparatus for producing silicon crystals respectively from silicon halogen compounds or halogen silanes can also be utilized as a reaction gas.
  • the reaction gas conducted to the first apparatus provided that it was in highly pure condition has due to the conversion in the first separation vessel a natural content of the hydrogen halide, so that the waste gas from the first vessel satisfies the requirements posed by the invention with respect to the reaction gas.
  • the content of HCl is frequently too slight, making it necessary to add further HCl to the waste gas.
  • HBr can be substituted for HCl.
  • the production of the hydrogen halide content of the initial gas by partial decomposition of a highly pure halogen-containing silicon compound can be eifected by hydrolysis or thermal decomposition as well as electrochemically.
  • a fresh mixture of a halogencontaining silicon compound and hydrogen can be partially converted by a stabilized high voltage gas discharge with formation of silicon halides and hydrogen halide, that is, for example, a chloride-containing silicon compound intermixed with hydrogen, and with the formation of silicon subchlorides and HCl.
  • the reaction gas consisting of hydrogen and silicon halide is for this purpose conducted in a steady flow through the gas discharge device and directly therefrom to the separation vessel.
  • the hydrogen halide content of the gas mixture can be adjusted to the desired value by the velocity of the gas stream and the voltage of the gas discharge.
  • a method of producing single crystal silicon consisting of the steps of contacting a carrier body of single crystal silicon with a stream of reaction gas adapted at elevated temperature for the separation of elementary silicon therefrom, heating said carrier body by electric cur-rent conducted therethrough to a temperature at which elementary silicon from the reaction gas is precipitated upon the solid surface parts of such carrier body and crystallizing to such surface parts, supplying to said reaction gas as an active ingredient a halogen silane, adding a gaseous hydrogen halide to the reaction gas prior to the contacting thereof with said carrier body, heating the latter during the separation procedure to the separation temperature, adjusting the carrier to a selected temperature at which silicon is separated from the reaction gas with the temperature being such that separation of silicon will be completely interrupted upon dropping of the carrier temperature to at most 200 C. below the selected separation temperature and upon further dropping of the carrier temperatures silicon of the carrier body will be dis-solved by the reaction gas.
  • reaction gas consists of SiCl mixed with hydrogen.
  • a method according to claim 5, comprising mixing a reaction gas consisting of hydrogen and 10 mole percent SiHCl with 10 mole percent HCl, and holding the temperature of the carrier body during the separation process substantially at 1150 C.
  • a method according to claim 7, comprising controlling the reduction of the reduction gas, for the production of the hydrogen halide content, so as to simultaneously produce thereby elementary silicon.
  • a method according to claim 7, comprising mixing a liquid silicon halogen compound with pure distilled water drop-wise added thereto, so that only part of the liquid halogen compound hydrolizes with water, contacting the resulting mixture with a stream of purified hydrogen gas, the hydrogen being thereby loaded with the vapor consisting of the silicon halogen compound and halogen hydrogen and being together with these vapors conducted into contact with the carrier body.
  • a method according to claim 7, comprising partially converting a mixture of a silicon halide compound and hydrogen, prior to contact thereof with the carrier body, by applying thereto a layer-stabilized high tension gas discharge with formation of silicon chlorides and hydrogen halide.
  • a method of producing single crystal silicon wherein a flowing reaction gas which contains a halogenized silane intermixed with purified hydrogen is caused to flow over an electrically heated single crystal carrier body made of pure or doped silicon, which body is disposed in a reaction vessel, the silicon thereby liberated from the reaction gas, respectively by thermal and electro-thermal conversion, being precipitated upon the carrier for single crystalline growth thereon; comprising the following steps, namely, admixing with a reaction gas, prior to conducting it into the reaction vessel which contains the heated carrier body, a gaseous hydrogen halide in such amount that silicon separation is obtained at the carrier surface at an adjusted predetermined carrier temperature which is maintained during the separation process, While the silicon separation is completely stopped upon decrease of the carrier temperature to a point lying at the most 200 C. below the adjusted temperature value and, upon further decrease of the carrier temperature, dissolving, by the re- 9 action gas, of precipitated silicon will take place.
  • waste gases, containing hydrogen halide, from an arrangement for producing highly pure silicon from a halogen silane are utilized as a basis forthe reaction gas.
  • a method according to claim 12, comprising conducting purified hydrogen to a vaporization vessel filled with liquid halogen silane, producing in said vessel. a hydrogen halide by feeding purified water thereinto in the form of drops, and thereupon conducting into the reaction vessel the hydrogen loaded with the hydrogen halide and vaporized residual halogen silane which has not been decomposed.
  • a method according to claim 12, comprising conducting, prior to the silicon separation, a fresh mixture which comprises adding the hydrogen chloride contained 7 in the waste gas of the same process to the reaction mixture supplied to the reaction vessel to thereby promote monocrystalline growthson the monoorystalline carrier body.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Silicon Compounds (AREA)
US81607A 1960-01-15 1961-01-09 Method of producing single crystal silicon Expired - Lifetime US3239372A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DES66651A DE1124028B (de) 1960-01-15 1960-01-15 Verfahren zum Herstellen von einkristallinem Silicium

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3330251A (en) * 1955-11-02 1967-07-11 Siemens Ag Apparatus for producing highest-purity silicon for electric semiconductor devices
US3341359A (en) * 1962-08-24 1967-09-12 Siemens Ag Process for pyrolytically precipitating elemental semiconductor substance
US3862020A (en) * 1970-12-07 1975-01-21 Dow Corning Production method for polycrystalline semiconductor bodies
DE3300716A1 (de) * 1982-01-12 1983-07-21 RCA Corp., 10020 New York, N.Y. Verfahren zum bilden von monokristallinem silicium auf einer maskenschicht
US4482422A (en) * 1982-02-26 1984-11-13 Rca Corporation Method for growing a low defect monocrystalline layer on a mask
US4549926A (en) * 1982-01-12 1985-10-29 Rca Corporation Method for growing monocrystalline silicon on a mask layer
US4578142A (en) * 1984-05-10 1986-03-25 Rca Corporation Method for growing monocrystalline silicon through mask layer
US4592792A (en) * 1985-01-23 1986-06-03 Rca Corporation Method for forming uniformly thick selective epitaxial silicon
US4698316A (en) * 1985-01-23 1987-10-06 Rca Corporation Method of depositing uniformly thick selective epitaxial silicon
US5463975A (en) * 1987-03-02 1995-11-07 Canon Kabushiki Kaisha Process for producing crystal
ES2331283A1 (es) * 2008-06-25 2009-12-28 Centro De Tecnologia Del Silicio Solar, S.L. (Centsil) Reactor de deposito de silicio de gran pureza para aplicaciones fotovoltaicas.

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2938772A (en) * 1955-07-29 1960-05-31 Wacker Chemie Gmbh Method of producing extremely pure silicon
US2943918A (en) * 1956-02-11 1960-07-05 Pechiney Prod Chimiques Sa Process for manufacturing dense, extra pure silicon

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2938772A (en) * 1955-07-29 1960-05-31 Wacker Chemie Gmbh Method of producing extremely pure silicon
US2943918A (en) * 1956-02-11 1960-07-05 Pechiney Prod Chimiques Sa Process for manufacturing dense, extra pure silicon

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3330251A (en) * 1955-11-02 1967-07-11 Siemens Ag Apparatus for producing highest-purity silicon for electric semiconductor devices
US3341359A (en) * 1962-08-24 1967-09-12 Siemens Ag Process for pyrolytically precipitating elemental semiconductor substance
US3862020A (en) * 1970-12-07 1975-01-21 Dow Corning Production method for polycrystalline semiconductor bodies
DE3300716A1 (de) * 1982-01-12 1983-07-21 RCA Corp., 10020 New York, N.Y. Verfahren zum bilden von monokristallinem silicium auf einer maskenschicht
US4549926A (en) * 1982-01-12 1985-10-29 Rca Corporation Method for growing monocrystalline silicon on a mask layer
US4482422A (en) * 1982-02-26 1984-11-13 Rca Corporation Method for growing a low defect monocrystalline layer on a mask
US4578142A (en) * 1984-05-10 1986-03-25 Rca Corporation Method for growing monocrystalline silicon through mask layer
US4592792A (en) * 1985-01-23 1986-06-03 Rca Corporation Method for forming uniformly thick selective epitaxial silicon
US4698316A (en) * 1985-01-23 1987-10-06 Rca Corporation Method of depositing uniformly thick selective epitaxial silicon
US5463975A (en) * 1987-03-02 1995-11-07 Canon Kabushiki Kaisha Process for producing crystal
ES2331283A1 (es) * 2008-06-25 2009-12-28 Centro De Tecnologia Del Silicio Solar, S.L. (Centsil) Reactor de deposito de silicio de gran pureza para aplicaciones fotovoltaicas.

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Publication number Publication date
CH426742A (de) 1966-12-31
NL271203A (da)
GB926807A (en) 1963-05-22
NL131048C (da)
GB1016578A (en) 1966-01-12
NL260072A (da)

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