US3015592A - Method of growing semiconductor crystals - Google Patents

Method of growing semiconductor crystals Download PDF

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Publication number
US3015592A
US3015592A US819766A US81976659A US3015592A US 3015592 A US3015592 A US 3015592A US 819766 A US819766 A US 819766A US 81976659 A US81976659 A US 81976659A US 3015592 A US3015592 A US 3015592A
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United States
Prior art keywords
melt
growing
crystal
upwards
semiconductor crystals
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US819766A
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Leopold Frans Martinus
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US Philips Corp
North American Philips Co Inc
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US Philips 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
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/10—Crucibles or containers for supporting the melt
    • C30B15/12—Double crucible methods
    • 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
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/005—Simultaneous pulling of more than one crystal

Definitions

  • the present invention relates to methods of making bodies, more particularly monocrystalline bodies, from semi-conductive material by drawing them upwards from a melt. Such a method has been described by Czochralsky in Zeitschrift fiir Physikalische Chemie, 92 (1917), pages 219 to 221.
  • the present invention has inter alia for its object to permit such bodies to be made with very few dislocations, and this more particularly by preventing as much as possible the occurrence of marginal eifects.
  • such bodies are drawn upwards from a melt while being surrounded by a tubular member consisting of the same material and being also immersed in the melt.
  • the temperature distribution inside the tubular body will be approximately the same as that in the body surrounded by it. This applies in particulate the inner faces and outer faces adjacent each other. This uniformity will be a maximum if the tubular body is drawn upwards simultaneously but, unless imposing the highest requirements, it is alternatively possible for this body to be stationary or even to make it melt slowly.
  • tubular bodies can be made in a simple manner by drawing them upwards, namely by immersing a tubular seed of the relevant material in the melt and by subsequently letting it grow in the same manner as was usual for solid rod-shaped bodies.
  • the material of the tubular member having more lattice defects than that of the rod-shaped body may be employed for uses imposing less stringent requirements or it may be melted up and Worked up again.
  • FIG. 1 shows schematically in a simplified manner a device for carrying out the invention and in which this device comprises a round crucible 1 in which provision is made of a partition 2 which is spaced from the outer wall, between which walls an annular space 3 is formed.
  • the semiconductive material for example germanium
  • the process is controlled so that the inside diameter of the tube 4 and the outside diameter of the rod 6 approach to each other as much as possible.
  • the partition 2 should only slightly overtop the surface of the melt. The partition 2 prevents the tubular member 4 from growing in the direction of its axis and uniting with the rod 6.
  • cooling will be low in a radial direction. This cooling will mainly occur in an axial direction, which results in the interface between the melt and the solidified mass being as planar as possible.
  • the level of the melt can be maintained constant by replenishment through an aperture in the wall. It may then be desirable locally to interrupt the partition 2, for example by providing one or more slots 7 in order that the level may remain the same at both sides. Alternatively, the spaces at both sides of the wall 2 may be filled up each separately, while the material in the space 5 may be purer than that in the space 3.
  • the prescription that the bodies 4 and 6 should consist of the same material is not to be understood to mean that there should be no difference in purity or in content of donors or acceptors, provided that their melting points and heat conductivity do not differ noticeably due .to such difierences.
  • a method of growing high-quality semiconductor crystals comprising the steps of providing a melt of semiconductor material, drawing a first growing tubular crystal upwards from the melt, and, simultaneously with the last step, drawing a second growing single crystal upwards from the melt within the first crystal and separate from the latter and such that it never extends beyond the first crystal.
  • a method of growing high-quality semiconductor crystals comprising the steps of providing a melt of semiconductor material, drawing a growing holiow cylindrical crystal upwards from the melt, and, simultaneously with the last step, drawing a growing crystal upwards from the melt and within the hollow cylindrical crystal.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)

Description

Jan. 2, 1962 F. M. LEOPOLD 3,015,592
METHOD OF GROWING SEMICONDUCTOR CRYSTALS Filed June 11, 1959 INVENTOR AGE United States Patent 3,015,592 METHOD OF GROWING SEMICONDUCTOR CRYSTALS Frans Martinus Leopold, Eindhoven, Netherlands, assignor to North American Philips Company, Inc., New
York, N.Y., a corporation of Delaware Filed June 11, 1959, Ser. No. 819,766 Claims priority, application Netherlands July 11, 1958 3 Claims. (Cl. 1481.6) e
The present invention relates to methods of making bodies, more particularly monocrystalline bodies, from semi-conductive material by drawing them upwards from a melt. Such a method has been described by Czochralsky in Zeitschrift fiir Physikalische Chemie, 92 (1917), pages 219 to 221.
It is known that, for obtaining rod-shaped bodies of regular shape, it is advantageous to rotate them about their longitudinal axis in drawing them upwards. Furthermore, it is known that the number of dislocations in the crystals produced is smaller as the liquid-solid interface approaches to a plane at right angles to said longi tudinal axis. In order to obtain such an interface special forms of heating elements have been proposed, while it has also been suggested to surround the liquid-solid interface by heat radiators and/ or reflectors.
The present invention has inter alia for its object to permit such bodies to be made with very few dislocations, and this more particularly by preventing as much as possible the occurrence of marginal eifects.
According to the invention, such bodies are drawn upwards from a melt while being surrounded by a tubular member consisting of the same material and being also immersed in the melt.
Viewed in a vertical direction or axial direction, the temperature distribution inside the tubular body will be approximately the same as that in the body surrounded by it. This applies in particulate the inner faces and outer faces adjacent each other. This uniformity will be a maximum if the tubular body is drawn upwards simultaneously but, unless imposing the highest requirements, it is alternatively possible for this body to be stationary or even to make it melt slowly.
It is known per se that such tubular bodies can be made in a simple manner by drawing them upwards, namely by immersing a tubular seed of the relevant material in the melt and by subsequently letting it grow in the same manner as was usual for solid rod-shaped bodies.
The material of the tubular member having more lattice defects than that of the rod-shaped body, may be employed for uses imposing less stringent requirements or it may be melted up and Worked up again.
In order that the invention may be readily carried into effect, an example will now be described in detail with reference to the accompanying drawing, which shows schematically in a simplified manner a device for carrying out the invention and in which this device comprises a round crucible 1 in which provision is made of a partition 2 which is spaced from the outer wall, between which walls an annular space 3 is formed. In this space, the semiconductive material, for example germanium, is melted, subsequently to which a semi-conductive, tubular member 4 is drawn upwards therefrom. For this pur- Patented Jan. 2, 1952 ICC ' sible and the process is controlled so that the inside diameter of the tube 4 and the outside diameter of the rod 6 approach to each other as much as possible. The partition 2 should only slightly overtop the surface of the melt. The partition 2 prevents the tubular member 4 from growing in the direction of its axis and uniting with the rod 6.
By now making provision that any part of the rod 6 is located opposite a part of the inner wall of the tube 4, cooling will be low in a radial direction. This cooling will mainly occur in an axial direction, which results in the interface between the melt and the solidified mass being as planar as possible.
The level of the melt can be maintained constant by replenishment through an aperture in the wall. It may then be desirable locally to interrupt the partition 2, for example by providing one or more slots 7 in order that the level may remain the same at both sides. Alternatively, the spaces at both sides of the wall 2 may be filled up each separately, while the material in the space 5 may be purer than that in the space 3. In this connection, the prescription that the bodies 4 and 6 should consist of the same material is not to be understood to mean that there should be no difference in purity or in content of donors or acceptors, provided that their melting points and heat conductivity do not differ noticeably due .to such difierences.
What is claimed is:
1. A method of growing high-quality semiconductor crystals, comprising the steps of providing a melt of semiconductor material, drawing a first growing tubular crystal upwards from the melt, and, simultaneously with the last step, drawing a second growing single crystal upwards from the melt within the first crystal and separate from the latter and such that it never extends beyond the first crystal.
2. A method of growing high-quality semiconductor crystals, comprising the steps of providing a melt of semiconductor material, drawing a growing holiow cylindrical crystal upwards from the melt, and, simultaneously with the last step, drawing a growing crystal upwards from the melt and within the hollow cylindrical crystal.
3. A method as set forth in claim 2, wherein the growing conditions are controlled such that the outer surface of the inner crystal is close to the inner surface of the hollow crystal.
References Cited in the file ofv this patent UNITED STATES PATENTS 2,730,470 Shockley Jan. 10, 1956 2,822,308 Hall Feb. 4, 1958 2,841,559 Rosi July 1, 1958 2,879,189 Shockley Mar. 24, 1959 FOREIGN PATENTS 962,553 Germany Apr. 25, 1957

Claims (1)

1. A METHOD OF GROWING HIGH-EQUALITY SEMICONDUCTOR CRYSTALS, COMPRISING THE STEPS OF PROVIDING A MELT OF SEMICONDUCTER MATERIAL, DRAWING A FIRST GROWING TUBULAR CRYSTAL UPWARDS FROM THE MELT, AND, SIMULTANEOUSLY WITH THE LAST STEP, DRAWING A SECOND GROWING SINGLE CRYSTAL UPWARDS FROM THE MELT WITHIN THE FIRST CRYSTAL AND SEPARATE FROM THE LATTER AND SUCH THAT IT NEVER EXTENDS BEYOND THE FIRST CRYSTAL.
US819766A 1958-07-11 1959-06-11 Method of growing semiconductor crystals Expired - Lifetime US3015592A (en)

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NL229533 1958-07-11

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DE (1) DE1108185B (en)
FR (1) FR1229489A (en)
GB (1) GB915120A (en)
NL (2) NL112257C (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3853489A (en) * 1971-11-08 1974-12-10 Tyco Laboratories Inc A non-wetting aid for growing crystalline bodies
US3876388A (en) * 1968-10-30 1975-04-08 Siemens Ag Method of varying the crystalline structure of or the concentration of impurities contained in a tubular starting crystal or both using diagonal zone melting
US3877880A (en) * 1971-07-31 1975-04-15 Kuhlmann Schafer Wilhelm Crystal melting apparatus fashioned to eliminate bubbles entrapped in the melt
US3915656A (en) * 1971-06-01 1975-10-28 Tyco Laboratories Inc Apparatus for growing crystalline bodies from the melt
US3961905A (en) * 1974-02-25 1976-06-08 Corning Glass Works Crucible and heater assembly for crystal growth from a melt
US4032390A (en) * 1974-02-25 1977-06-28 Corning Glass Works Plural crystal pulling from a melt in an annular crucible heated on both inner and outer walls
US4125425A (en) * 1974-03-01 1978-11-14 U.S. Philips Corporation Method of manufacturing flat tapes of crystalline silicon from a silicon melt by drawing a seed crystal of silicon from the melt flowing down the faces of a knife shaped heated element
US4190631A (en) * 1978-09-21 1980-02-26 Western Electric Company, Incorporated Double crucible crystal growing apparatus
US4289572A (en) * 1976-12-27 1981-09-15 Dow Corning Corporation Method of closing silicon tubular bodies
US4299648A (en) * 1980-08-20 1981-11-10 The United States Of America As Represented By The United States Department Of Energy Method and apparatus for drawing monocrystalline ribbon from a melt
US4469552A (en) * 1982-04-23 1984-09-04 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Process and apparatus for growing a crystal ribbon
US4647437A (en) * 1983-05-19 1987-03-03 Mobil Solar Energy Corporation Apparatus for and method of making crystalline bodies
US4711695A (en) * 1983-05-19 1987-12-08 Mobil Solar Energy Corporation Apparatus for and method of making crystalline bodies
US5021118A (en) * 1985-11-25 1991-06-04 Sumitomo Electric Industries, Ltd. Method of drawing-up a single crystal using a double-crucible apparatus and double-crucible apparatus and double-crucible apparatus therefor
US5069741A (en) * 1987-03-20 1991-12-03 Mitsubishi Kinzoku Kabushiki Kaisha Method of manufacturing quartz double crucible assembly

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL270246A (en) * 1961-10-13

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2730470A (en) * 1950-06-15 1956-01-10 Bell Telephone Labor Inc Method of making semi-conductor crystals
DE962553C (en) * 1954-09-14 1957-04-25 Licentia Gmbh Process for the production of monocrystalline semiconductor bodies in the form of hollow cylinders by drawing from the melt
US2822308A (en) * 1955-03-29 1958-02-04 Gen Electric Semiconductor p-n junction units and method of making the same
US2841559A (en) * 1955-04-27 1958-07-01 Rca Corp Method of doping semi-conductive materials
US2879189A (en) * 1956-11-21 1959-03-24 Shockley William Method for growing junction semi-conductive devices

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE973231C (en) * 1953-01-20 1959-12-24 Telefunken Gmbh Process for the production of single crystals by pulling from a melt
AT194444B (en) * 1953-02-26 1958-01-10 Siemens Ag Method and device for treating an elongated semiconductor crystal arrangement
DE1032852B (en) * 1953-11-24 1958-06-26 Siemens Und Halske Ag Process and device for the production of semiconductor crystals by the crystal pulling process from the melt
DE1044768B (en) * 1954-03-02 1958-11-27 Siemens Ag Method and device for pulling a rod-shaped crystalline body, preferably a semiconductor body

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2730470A (en) * 1950-06-15 1956-01-10 Bell Telephone Labor Inc Method of making semi-conductor crystals
DE962553C (en) * 1954-09-14 1957-04-25 Licentia Gmbh Process for the production of monocrystalline semiconductor bodies in the form of hollow cylinders by drawing from the melt
US2822308A (en) * 1955-03-29 1958-02-04 Gen Electric Semiconductor p-n junction units and method of making the same
US2841559A (en) * 1955-04-27 1958-07-01 Rca Corp Method of doping semi-conductive materials
US2879189A (en) * 1956-11-21 1959-03-24 Shockley William Method for growing junction semi-conductive devices

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3876388A (en) * 1968-10-30 1975-04-08 Siemens Ag Method of varying the crystalline structure of or the concentration of impurities contained in a tubular starting crystal or both using diagonal zone melting
US3915656A (en) * 1971-06-01 1975-10-28 Tyco Laboratories Inc Apparatus for growing crystalline bodies from the melt
US3877880A (en) * 1971-07-31 1975-04-15 Kuhlmann Schafer Wilhelm Crystal melting apparatus fashioned to eliminate bubbles entrapped in the melt
US3853489A (en) * 1971-11-08 1974-12-10 Tyco Laboratories Inc A non-wetting aid for growing crystalline bodies
US3961905A (en) * 1974-02-25 1976-06-08 Corning Glass Works Crucible and heater assembly for crystal growth from a melt
US4032390A (en) * 1974-02-25 1977-06-28 Corning Glass Works Plural crystal pulling from a melt in an annular crucible heated on both inner and outer walls
US4125425A (en) * 1974-03-01 1978-11-14 U.S. Philips Corporation Method of manufacturing flat tapes of crystalline silicon from a silicon melt by drawing a seed crystal of silicon from the melt flowing down the faces of a knife shaped heated element
US4289572A (en) * 1976-12-27 1981-09-15 Dow Corning Corporation Method of closing silicon tubular bodies
US4190631A (en) * 1978-09-21 1980-02-26 Western Electric Company, Incorporated Double crucible crystal growing apparatus
US4299648A (en) * 1980-08-20 1981-11-10 The United States Of America As Represented By The United States Department Of Energy Method and apparatus for drawing monocrystalline ribbon from a melt
US4469552A (en) * 1982-04-23 1984-09-04 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Process and apparatus for growing a crystal ribbon
US4647437A (en) * 1983-05-19 1987-03-03 Mobil Solar Energy Corporation Apparatus for and method of making crystalline bodies
US4711695A (en) * 1983-05-19 1987-12-08 Mobil Solar Energy Corporation Apparatus for and method of making crystalline bodies
US5021118A (en) * 1985-11-25 1991-06-04 Sumitomo Electric Industries, Ltd. Method of drawing-up a single crystal using a double-crucible apparatus and double-crucible apparatus and double-crucible apparatus therefor
US5069741A (en) * 1987-03-20 1991-12-03 Mitsubishi Kinzoku Kabushiki Kaisha Method of manufacturing quartz double crucible assembly

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NL229533A (en)
NL112257C (en)
GB915120A (en) 1963-01-09
DE1108185B (en) 1961-06-08
FR1229489A (en) 1960-09-07

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