US3648654A - Vertical liquid phase crystal growth apparatus - Google Patents

Vertical liquid phase crystal growth apparatus Download PDF

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Publication number
US3648654A
US3648654A US19929A US3648654DA US3648654A US 3648654 A US3648654 A US 3648654A US 19929 A US19929 A US 19929A US 3648654D A US3648654D A US 3648654DA US 3648654 A US3648654 A US 3648654A
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United States
Prior art keywords
substrate
container
melt
liquid phase
crystal growth
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Expired - Lifetime
Application number
US19929A
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English (en)
Inventor
Arpad Albert Bergh
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AT&T Corp
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Bell Telephone Laboratories Inc
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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
    • C30B19/00—Liquid-phase epitaxial-layer growth
    • C30B19/06—Reaction chambers; Boats for supporting the melt; Substrate holders
    • 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
    • C30B19/00—Liquid-phase epitaxial-layer growth
    • C30B19/06—Reaction chambers; Boats for supporting the melt; Substrate holders
    • C30B19/061—Tipping system, e.g. by rotation
    • 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
    • C30B19/00—Liquid-phase epitaxial-layer growth
    • C30B19/08—Heating of the reaction chamber or 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
    • C30B19/00—Liquid-phase epitaxial-layer growth
    • C30B19/10—Controlling or regulating
    • C30B19/106—Controlling or regulating adding crystallising material or reactants forming it in situ to the liquid

Definitions

  • a vertical liquid phase crystal growth apparatus includes (1) a container for housing a melt and either a single substrate or a plurality of substrates, (2) a furnace, and (3) a heat sink.
  • the melt and the substrates are isolated from one another prior to the growth process by means of a cover plate which restricts the free volume surrounding the substrate(s).
  • the container is heated to the desired temperature and the saturated melt containing the desired dopants and the substrate are allowed to come into contact by lifting the plate. Growth is then initiated from a convection-free melt by cooling the container and, thus, the substrate by means of a heat. sink which establishes a thermal gradient along the vertical axis of the container.
  • An apparatus which restricts the free volume surrounding the substrate and which physically separates the substrate from the melt would alleviate the first two above-mentioned causes of surface degradation. Since most impurities have a lower density than the usual melts employed in liquid phase growth, small particles of contamination usually float atop the melt. Apparatus has been developed heretofore in which the melt is skimmed" prior to contacting the substrate; however, the clean surface required entails extreme care, and it would be much easier and safer to construct an apparatus which prevents the substrate from contacting the liquid-gas interface, thereby eliminating the third above-mentioned cause of surface degradation.
  • convective currents in the melt during regrowth result in (I) an irregular thickness of the regrown surface, (2) a variable doping profile over the regrown layer and (3) a damaged interface between the substrate and the regrown layer. If cooling starts at the top of the melt or if regrowth is initiated at the top, gravity causes the heavier solution to sink and form convective cells. To avoid convection, a vertical temperature gradient must be established with a decreasing temperature toward the lowest part of the system. However, the apparatus should have a horizontal temperature gradient of zero in order to obtain a uniform thickness of the regrown layer.
  • the present invention is directed to a vertical liquid phase crystal growth apparatus, which optimizes the growth by (l) maintaining the free volume surrounding the substrate at a minimum, (2) physically segregating the substrate from the melt prior to growth, (3) preventing melt-substrate contact at the liquid-gas interface and (4) providing a vertical thermal gradient with isothermal conditions in the horizontal direction whereby the substrate is maintained at the lowest temperature.
  • the vertical apparatus consists of a container for housing a melt and a substrate.
  • the base of the container has a compartment or well which intimately accommodates the sides of the substrate.
  • Isolating the substrate from the melt when the container is maintained at an initial or first temperature is a cover plate which covers the substrate. Attached to the cover plate is a rod which raises the cover plate from the substrate when the container is maintained at a second temperature, thereby leading to contact between the substrate and the melt.
  • Covering the container is a lid which insures uniform heat dissipation from the container and through which the rod slidcably passes.
  • Contacting the base of the container is a heat sink which insures a vertical temperature gradient during growth.
  • a suitable substrate is placed in the container within the well.
  • the cover plate is placed over the substrate and a melt mixture containing the material to be grown and the required dopants is placed in the container atop and surrounding the cover plate.
  • the lid is affixed in place and the container is heated to a first temperature to form a solution from the melt mixture.
  • the cover plate is raised so as to uncover the substrate and allow the saturated melt to come in contact with and cover the substrate. Crystal growth is then allowed to proceed by cooling the substrate, employing a heat sink means.
  • a vertical temperature gradient is provided to insure deposition from a convection-free melt.
  • FIG. 1 is a perspective view of the vertical liquid phase crystal growth apparatus of the invention
  • FIG. 2 is a cross-sectional view of the growth container after being loaded with the substrate and the melt mixture
  • FIG. 3 is a cross-sectional view of the loaded container contained within the vertical furnace.
  • FIG. 4 is a cross-sectional view of the apparatus during crystal growth.
  • the materials may be selected from among group III(a)-V(a) compounds, group llI(b)-VI(a) compounds or group IV elements of the Periodic Table of the Elements as set forth in the Mendelyeev Periodic Table appearing on page B2 in the 45th edition of the Handbook of Chemistry and Physics, published by the Chemical Rubber Company.
  • FIG. 1 there is shown the vertical crystal growth apparatus of the present invention.
  • a container or boat 61 which can be fabricated from any inert material including such materials as high purity graphite, alumina, quartz, boron nitride, or any inert ceramic material. It is to be understood that all of the above-mentioned materials, including graphite, may or may not be employed with a high purity graphite liner (not shown). It is also to be understood that although the container or boat 61 has been shown to be rectangular in shape, the inventive concept need not be restricted thereby and the container may be parallelepiped or cylindrical in shape.
  • the container 61 has a compartment or well 62, on its base 63, destined for accommodating a substrate 64 flush against the walls 66 of the compartment 62. Covering the container 61 is a lid 67 which is constructed of the above-mentioned inert materials and which serves to insure uniform heat dissipation from the container 61.
  • Attached on one end 71 of the rod 68 is a cover plate 72 which may be made of any of the above-mentioned materials.
  • the cover plate 72 should be constructed of the substrate material, e.g., GaP, to decrease the surface degradation of the substrate via loss of any volatile elements therefrom and to assure a saturated melt. It is to be noted at this point, that when the substrate 64 has been inserted into container 61, the top surface 73 of the substrate 64 is almost flush with the top surface of the base 63. Therefore, when the cover plate 72 covers the substrate 64 (FIG.
  • the free volume 76 surrounding the substrate 64 is thereby maintained at a minimum. This minimization decreases the elemental loss due to evaporation from the substrate.
  • the free volume maintained should ideally be one which limits the loss due to evaporation to one monolayer of the surface of the substrate. The free volume is therefore dependent upon the substrate employed and the vapor pressures involved.
  • the container 61 is contained within a vertical furnace 74, supported therein by a pedestal 78.
  • a heat exchanger 79 is included within the furnace 74, as shown in FIGS. 1 and 3, wherein gas maintained at low temperatures is introduced via inlet 81 through the heat exchanger 79 and out through outlet 82.
  • the heat exchanger has been described in terms of a cooling gas exchanger, but the in-,
  • ventive embodiment is not to be restricted thereby and any heat sink means may be employed.
  • the apparatus may include a plurality of substrates accommodated within a plurality of compartments, all of which are within a single container and covered by either one large cover plate or a plurality of cover plates.
  • a suitable P-type GaP substrate material grown by standard liquid encapsulated pulling techniques is cut to size whereupon it is lapped and cleaned in accordance with conventional techniques.
  • the lapped and cleaned GaP substrate 64 is inserted into a high purity graphite container 61 similar to that described in FIG. 1. This loading is accomplished in an inert ambient such as nitrogen.
  • the substrate 64 is placed into well 62 and is thereupon covered by a cover plate 72 which is fabricated of GaP and to which is attached a high purity graphite rod 68.
  • a galliumGaPGa O -Zn melt mixture 75 is prepared by first weighing out high purity gallium, Zn and 03,0, obtained from commercial sources. The high resistivity GaP material is cut and weighed out and then added to the gallium, Zn and Ga O previously weighed out and the mixture 75 is added to the container 61 atop of the cover plate 72.
  • the amount of GaP employed is such as to form a saturated gallium solution at the desired temperature.
  • the composition meeting the saturation requirement is in the range of 0.2 to 12 mole percent GaP, in the temperature range of 800-1,200 C. v
  • a high purity graphite lid 67 is placed over the container 61, rod 68 passing through aperture 69 of the lid 67.
  • the lid 67 covers container 61 and insures uniform heat dissipation therefrom.
  • the container 61 is then placed within a standard vertical furnace 74 upon pedestal 78. Thermal insulation 84 is packed around the pedestal 78 thereby creating an isothermal center portion which accommodates the container 61.
  • the furnace 74 is flushed with nitrogen admitted to the system through suitable inlet and outlet means (not shown). After flushing with nitrogen, hydrogen is allowed to flow into the furnace 74 and the container 61 is heated to a first temperature above the melting point of gallium thereby resulting in the formation of a melt 83.
  • the substrate 64 is isolated or segregated from the melt 83 by means of the GaP cover plate 72 which prevents the transfer of volatile compounds to the substrate 64 prior to deposition.
  • the free volume 76 surrounding the substrate 64 is maintained ideally at 0.01 mm. to restrict the loss due to volatilization to approximately one monolayer of the surface of the Gal substrate 64.
  • the container 61 is heated to a second temperature in the range of 1,050-] ,060 C., resulting in the formation of a saturated P-type GaP gallium melt 83 doped with zinc and oxygen.
  • a second temperature in the range of 1,050-] ,060 C.
  • the cover plate 72 is lifted by raising rod 68 which results in the covering of the substrate 64 by the saturated melt 83. Due to the isothermal conditions, neither deposition on the substrate nor dissolution of the substrate occurs at this time. Also, the substrate is prevented from surface contamination via contact with the gas-melt interface.
  • a cooled inert gas such as nitrogen is flowed into inlet 81, through heat exchanger 79 and out through outlet 82. This causes the temperature of the pedestal 78, the base 63 and the substrate 64 contained within the container 61 to be lowered. A temperature gradient is established along the vertical axis of the container 61, the base 63 and the substrate 64 wherein the base 63' and the substrate 64 are at the lowest temperature. Crystal growth is thus initiated through the cooling of the saturated melt 83.
  • the growth process is terminated by lowering the cover plate 72 over the substrate 64.
  • the furnace 74 can be tilted, thereby tipping off the melt 83 from the substrate 64.
  • the GaP substrate 64 is in contact with the melt 83 from 4 to 50 minutes leading to a grown crystal layer of from A to 3 mils.
  • a vertical liquid phase epitaxial growth apparatus which comprises:
  • cover plate means closing off said compartment for isolating said substrate from said melt when said container is maintained at a first temperature, said cover means comprising a portion of the bottom support for said melt;
  • heat sink means contacting the base of said container for establishing a vertical temperature gradient along the vertical axis of said container.
  • said compartment is adapted to intimately accommodate the sides of said substrate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
US19929A 1970-03-16 1970-03-16 Vertical liquid phase crystal growth apparatus Expired - Lifetime US3648654A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US1992970A 1970-03-16 1970-03-16

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US3648654A true US3648654A (en) 1972-03-14

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Country Status (8)

Country Link
US (1) US3648654A (fr)
JP (1) JPS528796B1 (fr)
BE (1) BE764314A (fr)
DE (1) DE2111946C3 (fr)
FR (1) FR2084643A5 (fr)
GB (1) GB1315298A (fr)
NL (1) NL144496B (fr)
SE (1) SE377054B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4565156A (en) * 1982-03-01 1986-01-21 Zaidan Hojin Handotai Kenkyu Shinkokai Apparatus for performing solution growth relying on temperature difference technique
US6566277B1 (en) * 1999-09-22 2003-05-20 Canon Kabushiki Kaisha Liquid-phase growth method, liquid-phase growth apparatus, and solar cell
US20090095212A1 (en) * 2006-03-24 2009-04-16 Ngk Insulators, Ltd. Method for manufacturing single crystal of nitride

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3036317A1 (de) * 1980-09-26 1982-05-19 Licentia Patent-Verwaltungs-Gmbh, 6000 Frankfurt Verfahren und vorrichtung zur fluessigphasenepitaxie

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1422545A (en) * 1920-06-01 1922-07-11 Ernest L Dayton Coating apparatus
US3197328A (en) * 1961-11-15 1965-07-27 Boeing Co Fluidized bed generated by vibratory means
US3206322A (en) * 1960-10-31 1965-09-14 Morgan John Robert Vacuum deposition means and methods for manufacture of electronic components
US3382843A (en) * 1965-10-23 1968-05-14 Optical Coating Laboratory Inc Vacuum coating apparatus utilizing rotating sources
US3425878A (en) * 1965-02-18 1969-02-04 Siemens Ag Process of epitaxial growth wherein the distance between the carrier and the transfer material is adjusted to effect either material removal from the carrier surface or deposition thereon
US3491720A (en) * 1965-07-29 1970-01-27 Monsanto Co Epitaxial deposition reactor
US3524426A (en) * 1968-02-29 1970-08-18 Libbey Owens Ford Glass Co Apparatus for coating by thermal evaporation
US3551219A (en) * 1968-05-09 1970-12-29 Bell Telephone Labor Inc Epitaxial growth technique
US3560276A (en) * 1968-12-23 1971-02-02 Bell Telephone Labor Inc Technique for fabrication of multilayered semiconductor structure
US3565702A (en) * 1969-02-14 1971-02-23 Rca Corp Depositing successive epitaxial semiconductive layers from the liquid phase

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1422545A (en) * 1920-06-01 1922-07-11 Ernest L Dayton Coating apparatus
US3206322A (en) * 1960-10-31 1965-09-14 Morgan John Robert Vacuum deposition means and methods for manufacture of electronic components
US3197328A (en) * 1961-11-15 1965-07-27 Boeing Co Fluidized bed generated by vibratory means
US3425878A (en) * 1965-02-18 1969-02-04 Siemens Ag Process of epitaxial growth wherein the distance between the carrier and the transfer material is adjusted to effect either material removal from the carrier surface or deposition thereon
US3491720A (en) * 1965-07-29 1970-01-27 Monsanto Co Epitaxial deposition reactor
US3382843A (en) * 1965-10-23 1968-05-14 Optical Coating Laboratory Inc Vacuum coating apparatus utilizing rotating sources
US3524426A (en) * 1968-02-29 1970-08-18 Libbey Owens Ford Glass Co Apparatus for coating by thermal evaporation
US3551219A (en) * 1968-05-09 1970-12-29 Bell Telephone Labor Inc Epitaxial growth technique
US3560276A (en) * 1968-12-23 1971-02-02 Bell Telephone Labor Inc Technique for fabrication of multilayered semiconductor structure
US3565702A (en) * 1969-02-14 1971-02-23 Rca Corp Depositing successive epitaxial semiconductive layers from the liquid phase

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4565156A (en) * 1982-03-01 1986-01-21 Zaidan Hojin Handotai Kenkyu Shinkokai Apparatus for performing solution growth relying on temperature difference technique
US6566277B1 (en) * 1999-09-22 2003-05-20 Canon Kabushiki Kaisha Liquid-phase growth method, liquid-phase growth apparatus, and solar cell
US20090095212A1 (en) * 2006-03-24 2009-04-16 Ngk Insulators, Ltd. Method for manufacturing single crystal of nitride
US8025728B2 (en) * 2006-03-24 2011-09-27 Ngk Insulators, Ltd. Method for manufacturing single crystal of nitride

Also Published As

Publication number Publication date
DE2111946C3 (de) 1974-03-07
FR2084643A5 (fr) 1971-12-17
NL144496B (nl) 1975-01-15
BE764314A (fr) 1971-09-16
DE2111946A1 (de) 1971-09-30
GB1315298A (en) 1973-05-02
JPS528796B1 (fr) 1977-03-11
DE2111946B2 (de) 1973-08-02
NL7103418A (fr) 1971-09-20
SE377054B (fr) 1975-06-23

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