US3663320A - Vapor growth process for gallium arsenide - Google Patents

Vapor growth process for gallium arsenide Download PDF

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Publication number
US3663320A
US3663320A US846062A US3663320DA US3663320A US 3663320 A US3663320 A US 3663320A US 846062 A US846062 A US 846062A US 3663320D A US3663320D A US 3663320DA US 3663320 A US3663320 A US 3663320A
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Prior art keywords
gallium arsenide
substrate
crystal
layer
impurity
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US846062A
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Mitsuhiro Maruyama
Osamu Mizuno
Sadao Kikuchi
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NEC Corp
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Nippon Electric Co Ltd
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    • 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
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • 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
    • H01L21/02387—Group 13/15 materials
    • H01L21/02395—Arsenides
    • 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
    • H01L21/02538—Group 13/15 materials
    • H01L21/02546—Arsenides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S148/00—Metal treatment
    • Y10S148/007—Autodoping
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S148/00—Metal treatment
    • Y10S148/151—Simultaneous diffusion
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S438/00—Semiconductor device manufacturing: process
    • Y10S438/914—Doping
    • Y10S438/916—Autodoping control or utilization

Definitions

  • ABSTRACT A process is provided for vapor growing a gallium arsenide single crystal layer on a substrate seed-crystal of gallium arsenide having a uniform electron concentration profile in the layer wherein at least two kinds of impurities of the same conductivity type are employed, one which causes autodoping to occur in the vapor-grown crystal, the other which tends to inhibit autodoping.
  • U1 is IO m o 2 '4 lb Distance from the Boundary Face (micron) l8 2
  • FIG.2
  • This invention relates to a process of incorporating impurities in a substrate seed-crystal of gallium arsenide in order to attain a uniform electron concentration profile in the vaporgrown gallium arsenide epitaxial layer.
  • the resulting gallium arsenide crystal may be adapted for the fabrication of Gunn effect elements and other gallium arsenide devices.
  • the n-type impurities with which the substrate seed-crystals of gallium arsenide used for the vapor growth of gallium arsenide are doped are the elements of the Group VI of the Periodic Table, such as tellurium, sulfur and selenium and the Group IV elements, such as silicon and tin.
  • the tellurium concentration of the substrate is made low enough to prevent or inhibit the influence of the autodoping, the resistivity of the substrate is often too high for practical applications. Further, when a siliconor tin-doped substrate is used for the vapor growth, low electron concentration and an electrically high resistance region appear in the growth layer in the vicinity of the layer-substrate interface, with the result that the grown layer thus obtained also does not have a uniform electron concentration profile.
  • FIG. 1 is a graph showing typical electron concentration profiles of gallium arsenide epitaxial layers grown from the vapor phase on a conventional substrate seed-crystal;
  • FIG. 2 is a graph showing exemplary electron concentration profile of a grown layer on a substrate seed-crystal according to the present invention.
  • the present invention is directed to a process for doping a substrate seed-crystal of gallium arsenide with impurities, which overcomes the difficulties above mentioned and makes it possible to obtain a vapor grown layer having a uniform impurity concentration profile.
  • a substrate seed-crystal is employed for vapor growth which is doped with two kinds of impurities having the same conductivity type, one impurity being the type that causes autodoping into the grown layer from the substrate, the other being such as to inhibit autodoping.
  • the concentration of the first impurity which causes autodoping is sufficiently restricted so as to preclude autodoping during the growth process, while the concentration of the other impurity that inhibits autodoping is made as high as possible.
  • an epitaxial layer with uniform impurity concentration profile and of sufficiently low resistance is grown on the substrate.
  • the impurities that can cause autodoping into a grown layer are the n-type tellurium, selenium and sulfur and the p-type impurity zinc.
  • the other kind of impurities which tends to inhibit autodoping includes silicon, tin and germanium as n-type impurities, germanium being also a p-type impurity, since the germanium conductivity type is amphoteric.
  • the critical value is not affected by the conditions of the vapor growth of gallium arsenide and is about 5 l0"'cm'. There is no critical value for silicon and tin.
  • the high resistance region always appears in the growth layer in the vicinity of the layersubstrate interface, even if heavily siliconor tin-doped substrate is used, although the electron concentration of the substrate has an upper limit of about 3 l0 cm'
  • This invention is advantageous where the impurity concentration of the grown layer is SXIO cm or less if the grown layer is of the n-type.
  • a vapor-grown layer has an impurity concentration of more than 5Xl0cm the low electron concentration region in the vicinity of the layersubstrate interface does not appear, even if siliconor tindoped substrate is used; and, therefore, a substrate simply containing an impurity that does not cause autodoping results. This has nothing to do with the present invention. It is considered that there may be a similar concentration limit for ptype grown layer.
  • FIG. 1 graphically illustrates an example of electron concentration profile of an n-type vapor-grown layer on a conventional substrate of n-type gallium arsenide.
  • the curve 11 represents the electron concentration profile of a substrate.
  • the curve 13 is the electron concentration profile of the layer grown on a substrate doped with lXlO cm tellurium, which shows occurrence of autodoping of tellurium into the grown layer, while the curve 14 represents the profile of the layer grown on a substrate doped with l l0cm' silicon, which shows the appearance of low electron concentration region near the layer-substrate interface.
  • a substrate seed-crystal of n-type gallium arsenide doped with both 5 l0"cm tellurium and 1 1Ocm silicon is employed.
  • lines 21 and 22 represent electron concentrations in the substrate seed-crystal due to silicon and tellurium, respectively, while the hatched portion represents the amount of electron concentration due to silicon in excess of that due to tellurium.
  • an n-type gallium arsenide layer is grown by feeding arsenic trichloride (AsCl gas with hydrogen gas as a carrier gas into a reaction system in which gallium heated at 850 C. and the substrate heated at 750 C. are placed.
  • doping with silicon and tin both within the limit of concentration of about 3X10' cm' would make it possible to enhance the electron concentration of the substrate to 6X10cm"
  • Additional doping with tellurium and selenium both in the concentration of 5X10 cm would enable increasing the electron concentration of the substrate up to 7XlO cm without autodoping occuring in the grown layer.
  • the present invention makes it possible to obtain easily a vapor-grown layer of gallium arsenide having a uniform impurity concentration profile and to control, as desired, the impurity concentration profile in the growth layer near the layer-substrate interface by varying the kinds and concentration of the impurities doped in the substrate seedcrystal.
  • a process for vapor growing gallium arsenide which comprises, doping a substrate of gallium arsenide single crystal with at least one impurity selected from the group consisting of tellurium, selenium and sulfur each in an amount of about 5Xl0 m and at least one other impurity from the group consisting of silicon and tin, each in an amount of less than about SXIO Cm and vapor-growing an ntype gallium arsenide single crystal having impurity concentration of less than 5 l()m on said substrate of gallium arsenide single crystal.
  • the improvement which comprises the steps of doping said substrate seed-crystal with at least two kinds of impurities having the same conductivity type, one being able to cause antodoping to occur in the vapor-grown crystal which is selected from the group consisting of tellurium, selenium and sulfur each in an amount of about 5 l0"cm the other tending to inhibit autodoping which is selected from the group consisting of silicon, tin and germanium, and vapor-growing a gallium arsenide single crystal having impurity concentration of less than 5 l0cm on said substrate seed-crystal of gallium arsenide single crystal.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
US846062A 1968-08-02 1969-07-30 Vapor growth process for gallium arsenide Expired - Lifetime US3663320A (en)

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JP43055672A JPS4844395B1 (enrdf_load_stackoverflow) 1968-08-02 1968-08-02

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3793093A (en) * 1973-01-12 1974-02-19 Handotai Kenkyu Shinkokai Method for producing a semiconductor device having a very small deviation in lattice constant
US3849789A (en) * 1972-11-01 1974-11-19 Gen Electric Schottky barrier diodes
US3964089A (en) * 1972-09-21 1976-06-15 Bell Telephone Laboratories, Incorporated Junction transistor with linearly graded impurity concentration in the high resistivity portion of its collector zone
US4436769A (en) 1980-11-18 1984-03-13 British Telecommunications Metal organic vapor deposition procedure for preparing group III--V compounds on a heated substrate
US4574093A (en) * 1983-12-30 1986-03-04 At&T Bell Laboratories Deposition technique
US4792467A (en) * 1987-08-17 1988-12-20 Morton Thiokol, Inc. Method for vapor phase deposition of gallium nitride film
US5384151A (en) * 1993-08-11 1995-01-24 Northwestern University InGaAsP/GaAs diode laser
US5389396A (en) * 1993-08-11 1995-02-14 Northwestern University InGaAsP/GaAs diode laser
US5410178A (en) * 1994-08-22 1995-04-25 Northwestern University Semiconductor films

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3266952A (en) * 1960-07-14 1966-08-16 Hughes Aircraft Co Compound semiconductor devices
US3371051A (en) * 1965-06-22 1968-02-27 Rowland E. Johnson Intrinsic-appearing gallium arsenide compound semiconductor material
US3392193A (en) * 1964-11-18 1968-07-09 Texas Instruments Inc Gallium arsenide semiconductor doped with chromium and a shallow acceptor impurity
US3533967A (en) * 1966-11-10 1970-10-13 Monsanto Co Double-doped gallium arsenide and method of preparation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3266952A (en) * 1960-07-14 1966-08-16 Hughes Aircraft Co Compound semiconductor devices
US3392193A (en) * 1964-11-18 1968-07-09 Texas Instruments Inc Gallium arsenide semiconductor doped with chromium and a shallow acceptor impurity
US3371051A (en) * 1965-06-22 1968-02-27 Rowland E. Johnson Intrinsic-appearing gallium arsenide compound semiconductor material
US3533967A (en) * 1966-11-10 1970-10-13 Monsanto Co Double-doped gallium arsenide and method of preparation

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3964089A (en) * 1972-09-21 1976-06-15 Bell Telephone Laboratories, Incorporated Junction transistor with linearly graded impurity concentration in the high resistivity portion of its collector zone
US3849789A (en) * 1972-11-01 1974-11-19 Gen Electric Schottky barrier diodes
US3793093A (en) * 1973-01-12 1974-02-19 Handotai Kenkyu Shinkokai Method for producing a semiconductor device having a very small deviation in lattice constant
US4436769A (en) 1980-11-18 1984-03-13 British Telecommunications Metal organic vapor deposition procedure for preparing group III--V compounds on a heated substrate
US4574093A (en) * 1983-12-30 1986-03-04 At&T Bell Laboratories Deposition technique
US4792467A (en) * 1987-08-17 1988-12-20 Morton Thiokol, Inc. Method for vapor phase deposition of gallium nitride film
US5384151A (en) * 1993-08-11 1995-01-24 Northwestern University InGaAsP/GaAs diode laser
US5389396A (en) * 1993-08-11 1995-02-14 Northwestern University InGaAsP/GaAs diode laser
US5410178A (en) * 1994-08-22 1995-04-25 Northwestern University Semiconductor films
US5462008A (en) * 1994-08-22 1995-10-31 Northwestern University Semiconductor films

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