US3796548A - Boat structure in an apparatus for making semiconductor compound single crystals - Google Patents

Boat structure in an apparatus for making semiconductor compound single crystals Download PDF

Info

Publication number
US3796548A
US3796548A US00180041A US3796548DA US3796548A US 3796548 A US3796548 A US 3796548A US 00180041 A US00180041 A US 00180041A US 3796548D A US3796548D A US 3796548DA US 3796548 A US3796548 A US 3796548A
Authority
US
United States
Prior art keywords
seed
crystal
growth
boat
section
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 - Lifetime
Application number
US00180041A
Other languages
English (en)
Inventor
D Boss
E Hull
S Scilla
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Business Machines Corp
Original Assignee
International Business Machines Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by International Business Machines Corp filed Critical International Business Machines Corp
Application granted granted Critical
Publication of US3796548A publication Critical patent/US3796548A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/14—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method characterised by the seed, e.g. its crystallographic orientation
    • 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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/003—Heating or cooling of the melt or the crystallised material
    • 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
    • Y10S117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
    • Y10S117/90—Apparatus characterized by composition or treatment thereof, e.g. surface finish, surface coating
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
    • Y10T117/10—Apparatus
    • Y10T117/1024—Apparatus for crystallization from liquid or supercritical state
    • Y10T117/1092—Shape defined by a solid member other than seed or product [e.g., Bridgman-Stockbarger]

Definitions

  • ABSTRACT An apparatus useful for growing single crystal semiconductor material comprising a'liquid melt section coaxially integrated with a seed cavity and having an annularly disposed integral thermal reflector means and a radiant heat dissipating member horizontally disposed and in a post linear directionfrom the seed cavity.
  • This invention relates to apparatus for making single crystal semiconductor compounds and especially relates to a method and apparatus for the preparation of Group III-V single crystal compounds such as gallium arsenide ingots and slices thereof, suitable for use as semiconductor structures.
  • Doped and undoped single semiconductor crystals have been prepared or grown by a large variety of techniques. The most common involves the progressive, directional solidification of a molten semiconductor material from a starting seed crystal. The liquid is usually contained in a boat in .contact with said single crystal seed. The solid liquid interface is moved away from the seed by motion of the boat movement of the tempera-v ture gradient profile, or'by pulling the seed from the melt. These methodsare often referred to as the I-Iorizontal Bridgman, Gradient Freeze and the Czochralski techniques.
  • the boat containing the molten charge and a seed crystal of the desired orientation is situated in this gradient such that the point in the gradient corresponding to the melting temperature of the crystal is located at the pointatwhich the solid-liquid interface is desired during the seeding of the melt. Relative motion of the boat with respect to the gradient results in directional freezing of the crystal.
  • the melt is usually comprised of a molten compound of the approximate stoichiometry of the crystal to be grown as a single crystal.
  • the melt is usually held at a temperature above the melting point of the compound under an atmosphere of the more volatile elementat a pressure approximately equal to the dissociation pressure of the compound at its melting point.
  • Prior structures utilized in single crystal horizontal .growth did not maintain thermal symmetry about the crystal growth axis which hampered the desired and normal growth direction of the crystal along the horizontal axis of the boat. This condition nucleates unpredicted deviations from the normal growth axis which in turn voids the control of the geometry of the slice taken from the boule or ingot or results in polycrystalline growth,
  • these prior structures could not maintain the orientation of the seed crystal with respect to the longitudinal axis of theboat. This also affects the crystalline characteristics and geometry of slices taken from boules or ingots grown in these structures.
  • Seed cavities having a rectangular shape do not allow freedom of movement of the seed in' response to mechanical stress resulting from thermal .discontinuities surrounding the melt.
  • the seed becomes keyed in as a result of seed cavity wall distortions which results in stress being placed on the growing crystal due to differential thermal expansion.
  • Another object of this invention is to provide an apparatus for the monocrystalline growth of semiconductor material whereby the resultant boule or ingot is of such nature as to provide maximum control of the geometry of slices 'cut therefrom.
  • a monocrystalline semiconductor growth apparatus adaptable to providing a sharp temperature gradient at the solid-liquid interface of the crystal growth process and providing means for axially dissipating radiant heat energy from the hot to the cold segments of the process furnace and heating apparatus.
  • FIG. 1 is a perspective view of a boat apparatus for the growth of single crystal material showing a semicylindrical liquid containing section and an adjacent coaxial semi-conical section adjacent to said liquid containing section and the semi-cylindrical seed section or cavity with its associated radiant heat pipe and reflec-
  • FIG. 2 is a cross-sectional fragmented view of the crystal growing apparatus contained in a sealed tube which in turn is enclosed in a multizone furnace.
  • FIG. 3 is a cross-sectional fragmented view of the monocrystalline growing apparatus showing the liquid solid seed interface with the heat shield and the radiant heat dissipating member.
  • FIG. 4 is a fragmented top plan view showing the solid-liquid interface contained in the crystal growing apparatus and the associated heat shield and radiant energy conducting means.
  • FIG. 1 illustrates a specific configuration of the single crystal semiconductor crystal growing apparatus.
  • the apparatus is constructed of clear fused silica having a sand-blasted or roughened surface which avoids wetting of the interior surface by the molten liquid material.
  • the illustrative configuration of the liquid containing or melt section 1 is connected by a semi-conical coaxial transition section 2 to a coaxial semi-cylindrical seed containing section 3 of smaller radius than the melt section 1.
  • An integral tilted reflection member 4 annularly surrounding the seed cavity 3 near the center of seed 5 is provided.
  • Said reflecting means redirects radial heat flow from and about the conical coaxial section 2 backward and toward said section 2 illustrated in FIG. 4 by arrows 11; thereby preventing radial heat losses from the said conical section.
  • the resultant temperature stabilization prevents localized cold spots which produce polycrystalline nucleation which decreases the ultimate quality of the single crystal boule which in turn decreases yield.
  • the radiant energy conducting means 6 is a solid. cylinder of clean smooth and non-sandblasted fused silica having flame polished ends. This cylinder or light pipe conducts radiant energy longitudinally along the axis of the apparatus toward a colder furnace section subsequently explained and illustrated in reference to FIG. 2.
  • the apparatus constructed as illustrated and utilized in the process of single semiconductor crystal growth creates a radial thermal symmetry which enhances crystal growth along the horizontal axis of the apparatus without significant deviation therefrom.
  • FIG. 2 illustrates the crystal growing apparatus contained in a closed tube 7 which is in turn contained in a double or dual zone furnace arrangement whereby the hot'zone is maintained at a temperature to keep the molten material at 8 in a molten condition and sustains a solid liquid interface at 9 between the-molten polycrystalline material 8 and the solid seed 5.
  • the solid-liquid interface at 9 is maintained in a slightly convex configuration in the direction of the molten material.
  • This solid-liquid interface configuration results from the relatively higher horizontal heat flow with respect to the radial heat flow through the longitudinal heat conducting member 6 and illustrated by the arrows ll) in FIG. 4.
  • the interface configuration is concave toward the molten charge and detrimental to the growth of crystals with a high degree of perfection.
  • the single crystal growth apparatus of this invention is further described in connection with its application to the well known process for making doped or undoped gallium arsenide and known as the Horizontal Bridgman technique.
  • stoichiometric quantities of gallium and arsenic are reacted in a closedtube which is subjected to a temperature gradient of approximately 614 to 1,240C.
  • a double furnace apparatus as shown in FIG. 2 is provided having a cold zone 12 and a hot zone 13 and separated by an insulating partition 14.
  • a stoichiometric amount of polycrystalline gallium is placed in the liquid melt section 1 of the apparatus with a given amount of the desired dopant.
  • a previously prepared seed of the desired crystallographic orientation is inserted into the seed cavity.
  • the apparatus containing the aforesaid materials is placed in a tube with a sufficient amount of arsenic to maintain the stoichiometry of the melt plus an excess to maintain a condensed phase at one atmosphere of pressure at about 614C.
  • a seal off plug is inserted into the tube and the tube evacuated to 10" Torr, whereupon the tube is conventionally sealed off by collapsing the tube onto the plug.
  • the tube is now inserted into the furnace and brought to thermal equilibrium and positioned so that the gallium and dopant material are located in the hot section of the furnace and maintained in a molten state.
  • the liquid solid interface between the molten polycrystalline gallium and the seed crystal is located at a temperature of about 1,240C in the thermal gradient.
  • the tube is then moved at the desired crystal growth rate and with respect to the furnace from the hot zone toward the colder zone while maintaining the solidliquid interface between the molten gallium arsenide and the seed crystal within the said 1,240C temperature zone. This results in a horizontal directional freezing or crystallization of the charge.
  • the tube Upon completion of the crystallization of the molten charge, the tube is allowed to slowly cool to room temperature, whereby thermal shock is avoided, whereupon the tube is broken open and the apparatus containing the gallium arsenide ingot is removed.
  • the ingot or boule thus formed is preserved for further processing.
  • An apparatus for growing monocrystalline semiconductor material comprising a primary concave-boat section adapted to contain a melt and an integral concave end section having a decreased depth and width relative to said concave primary boat section and adapted to hold a seed crystal contacting said melt, the primary and end sections disposed axially, said end section having a disc shaped radiant heat reflecting means angularly and annularly disposed to the boat axis and a heat dissipating means secured in the distal portion of said end section and extending externally thereof and forming an end section closure.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
US00180041A 1971-09-13 1971-09-13 Boat structure in an apparatus for making semiconductor compound single crystals Expired - Lifetime US3796548A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US18004171A 1971-09-13 1971-09-13

Publications (1)

Publication Number Publication Date
US3796548A true US3796548A (en) 1974-03-12

Family

ID=22658988

Family Applications (1)

Application Number Title Priority Date Filing Date
US00180041A Expired - Lifetime US3796548A (en) 1971-09-13 1971-09-13 Boat structure in an apparatus for making semiconductor compound single crystals

Country Status (5)

Country Link
US (1) US3796548A (enExample)
JP (1) JPS5239389B2 (enExample)
DE (1) DE2241710C3 (enExample)
FR (1) FR2154458B1 (enExample)
GB (1) GB1343384A (enExample)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3944393A (en) * 1973-11-21 1976-03-16 Monsanto Company Apparatus for horizontal production of single crystal structure
US4169755A (en) * 1977-03-16 1979-10-02 U.S. Philips Corporation Growth of crystalline rods of gallium arsenide in a crucible of specially treated fibrous silicon dioxide
US4268483A (en) * 1976-03-17 1981-05-19 Metals Research Limited Improvements in and relating to the growth of crystalline material
US4572763A (en) * 1982-07-14 1986-02-25 Zaidan Hojin Handotai Kenkyu Shinkokai Method and apparatus for performing epitaxial growth of ZnSe crystal from a melt thereof
US4764350A (en) * 1986-10-08 1988-08-16 The United States Of America As Represented By The Secretary Of The Air Force Method and apparatus for synthesizing a single crystal of indium phosphide
US5248377A (en) * 1989-12-01 1993-09-28 Grumman Aerospace Corporation Crystal-growth furnace for interface curvature control
CN105297130A (zh) * 2014-06-03 2016-02-03 长春理工大学 下降法定向生长氟化物晶体的方法及装置
CN108546986A (zh) * 2018-04-19 2018-09-18 中国科学院半导体研究所 籽晶保护装置及单晶生长方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5276926U (enExample) * 1975-12-08 1977-06-08
JPS5722149U (enExample) * 1980-07-15 1982-02-04
JPS5722150U (enExample) * 1980-07-15 1982-02-04
JPS6090890A (ja) * 1983-10-24 1985-05-22 Mitsubishi Monsanto Chem Co 無機化合物単結晶の成長方法及び単結晶成長用ボ−ト
FR2614322B1 (fr) * 1987-04-27 1989-07-28 Europ Propulsion Four a gradient destine a la solidification orientee, notamment par la methode de bridgmann.

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3124489A (en) * 1960-05-02 1964-03-10 Method of continuously growing thin strip crystals
US3156533A (en) * 1960-07-26 1964-11-10 Imber Oscar Crystal growth apparatus
US3172734A (en) * 1957-03-07 1965-03-09 warren
US3198606A (en) * 1961-01-23 1965-08-03 Ibm Apparatus for growing crystals
US3210165A (en) * 1961-01-13 1965-10-05 Philips Corp Zone-melting treatment of semiconductive materials
US3240568A (en) * 1961-12-20 1966-03-15 Monsanto Co Process and apparatus for the production of single crystal compounds
US3401022A (en) * 1964-03-26 1968-09-10 Motorola Inc Apparatus for horizontal zone refining of semiconductive materials
US3453352A (en) * 1964-12-14 1969-07-01 Texas Instruments Inc Method and apparatus for producing crystalline semiconductor ribbon
US3464812A (en) * 1966-03-29 1969-09-02 Massachusetts Inst Technology Process for making solids and products thereof
US3520810A (en) * 1968-01-15 1970-07-21 Ibm Manufacture of single crystal semiconductors
US3607054A (en) * 1969-05-05 1971-09-21 Us Army Method for extending the growth of vapor-liquid-solid grown crystals
US3617223A (en) * 1968-05-21 1971-11-02 Texas Instruments Inc Apparatus for forming monocrystalline ribbons of silicon

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3172734A (en) * 1957-03-07 1965-03-09 warren
US3124489A (en) * 1960-05-02 1964-03-10 Method of continuously growing thin strip crystals
US3156533A (en) * 1960-07-26 1964-11-10 Imber Oscar Crystal growth apparatus
US3210165A (en) * 1961-01-13 1965-10-05 Philips Corp Zone-melting treatment of semiconductive materials
US3198606A (en) * 1961-01-23 1965-08-03 Ibm Apparatus for growing crystals
US3240568A (en) * 1961-12-20 1966-03-15 Monsanto Co Process and apparatus for the production of single crystal compounds
US3401022A (en) * 1964-03-26 1968-09-10 Motorola Inc Apparatus for horizontal zone refining of semiconductive materials
US3453352A (en) * 1964-12-14 1969-07-01 Texas Instruments Inc Method and apparatus for producing crystalline semiconductor ribbon
US3464812A (en) * 1966-03-29 1969-09-02 Massachusetts Inst Technology Process for making solids and products thereof
US3520810A (en) * 1968-01-15 1970-07-21 Ibm Manufacture of single crystal semiconductors
US3617223A (en) * 1968-05-21 1971-11-02 Texas Instruments Inc Apparatus for forming monocrystalline ribbons of silicon
US3607054A (en) * 1969-05-05 1971-09-21 Us Army Method for extending the growth of vapor-liquid-solid grown crystals

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3944393A (en) * 1973-11-21 1976-03-16 Monsanto Company Apparatus for horizontal production of single crystal structure
US4268483A (en) * 1976-03-17 1981-05-19 Metals Research Limited Improvements in and relating to the growth of crystalline material
US4169755A (en) * 1977-03-16 1979-10-02 U.S. Philips Corporation Growth of crystalline rods of gallium arsenide in a crucible of specially treated fibrous silicon dioxide
US4572763A (en) * 1982-07-14 1986-02-25 Zaidan Hojin Handotai Kenkyu Shinkokai Method and apparatus for performing epitaxial growth of ZnSe crystal from a melt thereof
US4968491A (en) * 1982-07-14 1990-11-06 Zaidan Hojin Handotai Kenkyu Shinkokai Apparatus for performing epitaxial growth of ZNSE crystal from melt thereof
US4764350A (en) * 1986-10-08 1988-08-16 The United States Of America As Represented By The Secretary Of The Air Force Method and apparatus for synthesizing a single crystal of indium phosphide
US5248377A (en) * 1989-12-01 1993-09-28 Grumman Aerospace Corporation Crystal-growth furnace for interface curvature control
CN105297130A (zh) * 2014-06-03 2016-02-03 长春理工大学 下降法定向生长氟化物晶体的方法及装置
CN108546986A (zh) * 2018-04-19 2018-09-18 中国科学院半导体研究所 籽晶保护装置及单晶生长方法
CN108546986B (zh) * 2018-04-19 2020-09-15 中国科学院半导体研究所 籽晶保护装置及单晶生长方法

Also Published As

Publication number Publication date
JPS4840374A (enExample) 1973-06-13
GB1343384A (en) 1974-01-10
DE2241710C3 (de) 1980-10-23
DE2241710B2 (de) 1980-03-06
JPS5239389B2 (enExample) 1977-10-05
DE2241710A1 (de) 1973-03-22
FR2154458B1 (enExample) 1978-08-04
FR2154458A1 (enExample) 1973-05-11

Similar Documents

Publication Publication Date Title
US3796548A (en) Boat structure in an apparatus for making semiconductor compound single crystals
CN113322510B (zh) SiC单晶生长装置及液相外延SiC单晶生长方法
US4264406A (en) Method for growing crystals
US4840699A (en) Gallium arsenide crystal growth
JP2009149452A (ja) 半導体結晶成長方法
US5064497A (en) Crystal growth method and apparatus
US4096025A (en) Method of orienting seed crystals in a melt, and product obtained thereby
US5431125A (en) Twin-free crystal growth of III-V semiconductor material
US4764350A (en) Method and apparatus for synthesizing a single crystal of indium phosphide
JP2002293686A (ja) 化合物半導体単結晶の成長方法及びそれから切り出した基板
EP1114884A1 (en) Process for producing compound semiconductor single crystal
US4824519A (en) Method and apparatus for single crystal pulling downwardly from the lower surface of a floating melt
JP2009190914A (ja) 半導体結晶製造方法
US4963334A (en) High temperature heat pipe coracle and process
JPH1129398A (ja) 化合物半導体単結晶の製造装置
JPS62265193A (ja) 化合物半導体単結晶の製造方法及び装置
JPH0474788A (ja) 化合物半導体単結晶の製造方法
JP2781856B2 (ja) 化合物半導体単結晶の製造方法
JPH02229791A (ja) 化合物半導体単結晶製造装置
JPH03137085A (ja) ２―６族化合物半導体結晶の製造方法
JP2006169037A (ja) 化合物半導体単結晶の製造方法
JPH07206584A (ja) 化合物半導体単結晶の製造方法
NISHINAGA et al. Rapid Melt Growth of Ge by TR-IA Sounding Rocket
JPH10182277A (ja) 単結晶製造装置及びそれを用いた単結晶製造方法
JPH0631192B2 (ja) 半導体単結晶の製造方法及び装置