US3445300A - Method of epitaxial deposition wherein spent reaction gases are added to fresh reaction gas as a viscosity-increasing component - Google Patents

Method of epitaxial deposition wherein spent reaction gases are added to fresh reaction gas as a viscosity-increasing component Download PDF

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Publication number
US3445300A
US3445300A US524200A US3445300DA US3445300A US 3445300 A US3445300 A US 3445300A US 524200 A US524200 A US 524200A US 3445300D A US3445300D A US 3445300DA US 3445300 A US3445300 A US 3445300A
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reaction
viscosity
added
gas
gases
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US524200A
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English (en)
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Erhard Sirtl
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Siemens AG
Siemens Corp
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Siemens Corp
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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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02373—Group 14 semiconducting materials
    • H01L21/02381—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD

Definitions

  • My invention relates to a method of growing uniform epitaxial layers of semiconductor material, especially but not exclusively silicon, by pyrolytically dissociating a gaseous compound of the semiconductor material, and precipitating the evolving semiconductor material upon a heated monocrystalline substrate preferably consisting of the same material.
  • I modify the above-mentioned pyrolytic dissociation and precipitation process by admixing to the reaction gas a viscosity-increasing additional component whose molar 3,445,300 Patented May 20, 1969 weight is considerably higher than that of hydrogen, preferably amounting to a multiple of the hydrogen molar weight, the added component being chosen from gaseous materials that are inert with respect to the pyrolytic reaction.
  • a reaction gas for example, is a mixture of a halogen compound or a hydrogen-halogen compound of the semiconductor material to be precipitated, this compound being used in mixture with hydrogen.
  • silicochloroform may be used for producing epitaxial layers of silicon.
  • Suitable as viscosity-increasing addition to the reaction gas are gases, such as nitrogen, argon or krypton, that are inert at the reaction temperature.
  • gases such as nitrogen, argon or krypton
  • the partially spent residual gases resulting from the method according to the invention are recycled back to the fresh-gas supply in order to increase the viscosity of the reaction-gas mixture applied to the heated substrate.
  • silicochloroform As gaseous semicon ductor compound, it has been found favorable to provide for a molar mixing ratio of silicochloroform to hydrogen in the range from about 0.01 to 0.1.
  • the amount of the added component may then be approximately 5 to 50 mole percent, preferably 20 to 30 mole percent, of the hydrogen quantity being supplied.
  • the additional component may be admixed to the reaction gas immediately from the beginning of the pyrolytic process.
  • Another mode of performing the method of the invention is to add the viscosity-increasing component only at a subsequent stage, preferably after a preceding annealing process. The latter mode is particularly advantageous when using nitrogen as highviscosity component.
  • the reaction gas may be given an addition of doping substance.
  • the quantity of the admixed doping material may be kept constant during the course of the reaction or it may be varied during the reaction.
  • Semiconductor material made by the method according to the invention is particularly favorable for the production of electronic semiconductor devices such as transistors, rectifiers or the like.
  • the substrates provided with these layers can be subjected to further fabrication into semiconductor devices virtually without mechanical machining of the layers.
  • FIG. 1 shows schematically and partly in section an apparatus for performing the method of the invention.
  • FIG. 2 shows schematically a cross section of a silicon wafer made according to the invention
  • FIG. 3 shows schematically and for comparison a cross section typical of products resulting from known methods.
  • FIGS. 4 and 5 respectively show in cross section two groups of semiconductor discs made by the method of the invention and by prior methods respectively.
  • the apparatus illustrated in FIG. 1 comprises a reaction vessel 1 of quartz or quartz glass in which a substrate body 2 of n-type silicon is placed upon the top of a heater 3.
  • the electric leads 4 and 5.of the heater 3 are connected to respective terminals 6 and 7 on the outside of the reaction vessel for attachment to a voltage source.
  • the vessel 1 has an inlet 8 for supplying the reaction-gas mixture, and an outlet nipple 9 through which the residual gases leave the vessel.
  • the vessel is supplied with a reaction-gas mixture entering in the direction of the arrow 10.
  • the mixture is composed of vaporous semiconductor compound, hydrogen and an addition of argon.
  • silicochloroform is employed as the semiconductor compound to be dissociated.
  • the gaseous compound is obtained by evaporating the liquid compound in an evaporator vessel 11 located within a temperature control bath 110.
  • Hydrogen is introduced into the evaporator vessel 11 from a storage bottle 13 past an overpressure relief valve 130.
  • the additive argon is introduced from a storage bottle 14 communicating with another overpressure relief valve 140.
  • Control valves 15 and 16 for hydrogen and argon permit selectively a simultaneous or successive supply of these two gases.
  • a cooling trap 12 connected in the gas path ahead of evaporator vessel 11 removes any liquid from the entering gases.
  • Flow meters 17 and. 18 indicate the quantities of the respective gases being supplied.
  • the apparatus is further equipped with stop valves 19 and 20 with Whose aid the reaction vessel 1 can be sealed off.
  • a mixture of silicochloroform and hydrogen in a. molar ratio of 0.3 is being used. Added to this mixture are about mole percent argon. This mixture enters in the direction of the arrow 10 into the reaction vessel 1 where it is dissociated at the substrate 2 heated to a temperature of 1130 C. The evolving silicon precipitates onto the substrate 2.
  • the epitaxial layer thus grown on the substrate surface exhibits an extremely uniform constitution.
  • the layer thickness is virtually independent of the flow direction of the gas. If several substrate Wafers are simultaneously processed instead of only one substrate, they show virtually no dilference in layer thickness between each other. This result is represented in FIGS. 2, 3 and 4, 5.
  • FIG. 2 shows schematically and by way of example a silicon circular disc 21 made by the method of the invention.
  • the thickness values d d in FIG. 2 and the corresponding values d and 11 in FIG. 3 are greatly exaggerated as to absolute dimensions and their ratio to the disc diameter.
  • Denoted by d is the layer thickness at the side where the fresh gas first reaches the semiconductor body 21.
  • a semiconductor disc 31 as shown in FIG. 3 which is made by the conventional method without the addition of a viscosityincreasing component, has a much larger thickness d at the incoming side of the gas flow than at the opposite side.
  • FIGS. 4 and 5 represent the analogous conditions obtaining with a simultaneous production of several semiconductor discs which are denoted by 41 in FIG. 4 and by 51 in FIG. 5.
  • the semiconductor discs made by the method of the invention have equal layer thicknesses d and d regardless of the particular locality of the substrates, whereas the conventional method results in semiconductor discs whose respective thicknesses d and 0. exhibit considerable differences.
  • the residual gases resulting from the dissociation reaction may also be employed as additional viscosity-increasing components.
  • the spent waste gases from the reaction vessel are cycled back into the reaction vessel so that they again enter into the dissociation-reaction space together with the fresh reaction gas.
  • This expedient is not by far as generally applicable as the addition of heavy gases that do not participate in the reaction, such as nitrogen at temperatures below 1300 C., or generally argon and other noble gases.
  • reaction gas is a mixture of silicochloroform and hydrogen in a molar mixing ratio between 0.01 and 0.1.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical Vapour Deposition (AREA)
  • Silicon Compounds (AREA)
US524200A 1965-02-05 1966-02-01 Method of epitaxial deposition wherein spent reaction gases are added to fresh reaction gas as a viscosity-increasing component Expired - Lifetime US3445300A (en)

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US (1) US3445300A (enrdf_load_stackoverflow)
AT (1) AT259019B (enrdf_load_stackoverflow)
CH (1) CH476515A (enrdf_load_stackoverflow)
DE (1) DE1544259A1 (enrdf_load_stackoverflow)
GB (1) GB1135111A (enrdf_load_stackoverflow)
NL (1) NL6601149A (enrdf_load_stackoverflow)
SE (1) SE309223B (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3941647A (en) * 1973-03-08 1976-03-02 Siemens Aktiengesellschaft Method of producing epitaxially semiconductor layers
US4370158A (en) * 1978-10-04 1983-01-25 Heraeus Quarzschmelze Gmbh Heat-treating method for semiconductor components

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2910394A (en) * 1953-10-02 1959-10-27 Int Standard Electric Corp Production of semi-conductor material for rectifiers
US3152933A (en) * 1961-06-09 1964-10-13 Siemens Ag Method of producing electronic semiconductor devices having a monocrystalline body with zones of respectively different conductance
US3173814A (en) * 1962-01-24 1965-03-16 Motorola Inc Method of controlled doping in an epitaxial vapor deposition process using a diluentgas
US3197411A (en) * 1962-07-09 1965-07-27 Bell Telephone Labor Inc Process for growing gallium phosphide and gallium arsenide crystals from a ga o and hydrogen vapor mixture
US3200018A (en) * 1962-01-29 1965-08-10 Hughes Aircraft Co Controlled epitaxial crystal growth by focusing electromagnetic radiation
US3297501A (en) * 1963-12-31 1967-01-10 Ibm Process for epitaxial growth of semiconductor single crystals
US3354004A (en) * 1964-11-17 1967-11-21 Ibm Method for enhancing efficiency of recovery of semi-conductor material in perturbable disproportionation systems
US3382113A (en) * 1964-07-25 1968-05-07 Ibm Method of epitaxially growing silicon carbide by pyrolytically decomposing sih4 and ch4

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2910394A (en) * 1953-10-02 1959-10-27 Int Standard Electric Corp Production of semi-conductor material for rectifiers
US3152933A (en) * 1961-06-09 1964-10-13 Siemens Ag Method of producing electronic semiconductor devices having a monocrystalline body with zones of respectively different conductance
US3173814A (en) * 1962-01-24 1965-03-16 Motorola Inc Method of controlled doping in an epitaxial vapor deposition process using a diluentgas
US3200018A (en) * 1962-01-29 1965-08-10 Hughes Aircraft Co Controlled epitaxial crystal growth by focusing electromagnetic radiation
US3197411A (en) * 1962-07-09 1965-07-27 Bell Telephone Labor Inc Process for growing gallium phosphide and gallium arsenide crystals from a ga o and hydrogen vapor mixture
US3297501A (en) * 1963-12-31 1967-01-10 Ibm Process for epitaxial growth of semiconductor single crystals
US3382113A (en) * 1964-07-25 1968-05-07 Ibm Method of epitaxially growing silicon carbide by pyrolytically decomposing sih4 and ch4
US3354004A (en) * 1964-11-17 1967-11-21 Ibm Method for enhancing efficiency of recovery of semi-conductor material in perturbable disproportionation systems

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3941647A (en) * 1973-03-08 1976-03-02 Siemens Aktiengesellschaft Method of producing epitaxially semiconductor layers
US4370158A (en) * 1978-10-04 1983-01-25 Heraeus Quarzschmelze Gmbh Heat-treating method for semiconductor components

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Publication number Publication date
NL6601149A (enrdf_load_stackoverflow) 1966-08-08
DE1544259A1 (de) 1970-07-09
SE309223B (enrdf_load_stackoverflow) 1969-03-17
GB1135111A (en) 1968-11-27
AT259019B (de) 1967-12-27
CH476515A (de) 1969-08-15

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