US3020132A - Single crystal refining - Google Patents

Single crystal refining Download PDF

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Publication number
US3020132A
US3020132A US809957A US80995759A US3020132A US 3020132 A US3020132 A US 3020132A US 809957 A US809957 A US 809957A US 80995759 A US80995759 A US 80995759A US 3020132 A US3020132 A US 3020132A
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United States
Prior art keywords
molten
heat
zone
single crystal
refining
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
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US809957A
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English (en)
Inventor
Gerard R Gunther-Mohr
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
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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
Priority to NL112210D priority Critical patent/NL112210C/xx
Priority to NL250835D priority patent/NL250835A/xx
Priority to US809957A priority patent/US3020132A/en
Application filed by International Business Machines Corp filed Critical International Business Machines Corp
Priority to US809956A priority patent/US3036898A/en
Priority to FR817453A priority patent/FR1263807A/fr
Priority to GB14353/60A priority patent/GB915732A/en
Priority to FR825549A priority patent/FR1263881A/fr
Priority to DEJ22966A priority patent/DE1243145B/de
Priority to DEJ18050A priority patent/DE1150357B/de
Application granted granted Critical
Publication of US3020132A publication Critical patent/US3020132A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/02—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist
    • D02G1/0206—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist by false-twisting
    • D02G1/0266—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist by false-twisting false-twisting machines
    • 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
    • C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
    • C30B13/16—Heating of the molten zone
    • C30B13/22—Heating of the molten zone by irradiation or electric discharge
    • C30B13/24—Heating of the molten zone by irradiation or electric discharge using electromagnetic waves
    • 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
    • Y10S148/074—Horizontal melt solidification
    • 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
    • Y10T117/1076—Apparatus for crystallization from liquid or supercritical state having means for producing a moving solid-liquid-solid zone
    • Y10T117/108—Including a solid member other than seed or product contacting the liquid [e.g., crucible, immersed heating element]
    • 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
    • Y10T117/1076—Apparatus for crystallization from liquid or supercritical state having means for producing a moving solid-liquid-solid zone
    • Y10T117/1088—Apparatus for crystallization from liquid or supercritical state having means for producing a moving solid-liquid-solid zone including heating or cooling details

Definitions

  • a most widely used one of these techniques involves the principle that an impurity hasa greater afilnity for the molten state than the solid state so that a molten region may be employed to sweep out of a quantity of a material all impurities present therein so'that a very closely controlled quantity of the proper type of impurities may be'added at a later step.
  • the high purity refining technique has been developed considerably in connection with the semiconductor art. As the art has thus far developed, there have been two variations of this technique employed to provide semiconductor material useful in transistor and other semiconductor device manufacturing. These variations have been known as zone refining where the molten region is employed to purify the material, and, zone leveling" where the molten region is employedto evenly distribute a given. quantity of a articular impurity throughout a quantity of semiconductor material.
  • zone reilining hasbeen described in the publication The Transactions'of the American institute of Metallurgical Engineers, vol. 194, page 141, 1952, by W. G. Pfann.
  • zone leveling is described in the Bell SystemTechnical Journal, vol. 35, page 637, 1956, by D. C. Bennett and B. Sawyer.
  • zone refining and/or levelingoperation may be combined with a proper arrangement of conditions of heat application and seed shielding structure to result in the growth of a single crystal of material between all molten zone passes in a single operation which operates to control the variation of the segregation coefficient due to segregation at grain boundaries and thereby to attaina higher degree of crystal purity than has heretofore been available in the art.
  • a container with V a charge of a material capable of being zone refined and capable of absorbing infra-red energy.
  • a material capable of being zone refined and capable of absorbing infra-red energy.
  • organic compounds such as anthracene and many dielectrics.
  • semiconductor material undergoing a single crystal refining operation in accordance with the invention has been selected.
  • the semiconductor material is labeled element 1 and is illustrated in an intermediate stage of refining wherein the material 1 is shown as having an unrefined portion 1A, two partially refined single crystal portions 113, and a refined portion 1C. a Each of these portions is separated from its adjacent portion by a molten zone ID.
  • the semiconductor material- may be any material in which the impurities have a greater afilnity for the liquid state than the solid state and which have a monocrystalline form
  • the monoatomic semiconductors such as germanium and a silicon and the intermetallic compounds such as indium antimonide are examples.
  • section 1A is shown as being an amorphous group of particles and, of unrefined semiconductor ma terial, when a first molten zone passes, it is transformed into a single crystal section lBa andwherein molten zone lDa contains a large quantity of impurities present.
  • the second molten zone labelled lDb in passing further refines the semiconductor material.
  • the third illustrated molten zone labelled 1Dc still further refines the semiconductor material and as each molten zone progresses serially away from the seed crystal, the molten semiconductor material solidifies in an epitaxial manner on the seed crystal 1C, and, as each molten zone progresses along the length of the material 1, a single crystal of spanner:
  • a heat source which for example, may be by way of elliptical radiant heater reflectors 4, arranged in sufficient plurality for the number of molten zone processes desired. It has been found advantageous for uniform heat transmission to provide the reflectors in pairs. In the case of the pair of reflectors 4A, these sources provide sufficient heat for the first molten zone lDa.
  • the pair of radiant heaters 43 provide sufiicientheat for the second molten zone lDb and the pair of radiant heaters 4C provide suificient heat for the third illustrated molten zone lDc.
  • a heat control is provided for the seed enabling the seed to pass through the heating zones and to permit formation of a single crystal between each molten zone thereby keeping the segregation coeflicient from being influenced by grain boundary formation and reducing the amount of the seed that is melted to contaminate the refined material.
  • a heat control 5 is provided to control the temperature of the seed crystal 10, the freezing interface, and to prevent the heat from the radiant heaters 4 applying the heat to the seed crystal when it passes under the heaters.
  • the sources of heat 4 may be in addition to the radiant heaters illustrated, any sumciently intense and controllable source of heat capable of producing a defined molten region in the semiconductor material.
  • the heat controlling element 5 may be any structural arrangement that is capable of exercising. in the region of the seed and the freezing interface, a control on the amount of heat transferred from the heating source to the semiconductor material.
  • the element 5 serves a dual purpose in that it prevents direct heat application to the seed- 1C where it is drawn through a heated region and it controls heat dissipation in the vicinity of the freezing interface by reducing the temperature gradient thereby providing better quality crystals.
  • the dimension of the width of the molten zone in practice is found to be quite critical in that it determines the number of molten zones that can traverse a given quantity of semiconductor material in a single pass, and the maximum purity achievable.
  • the molten zone width must be approximately equal to the bar thickness in order to insure that all the material is melted in each pass of amoltenzone. It is found that the radiant heaters are quite convenient in that they can be focused to provide a very narrow molten region.
  • the molten zone length in practice is of the order of 0.2 inch, and, in the case of the tech nique known in the art as floating zone refining, the molten zones ID are sufficiently narrow that surface tension of the molten material tends to hold it in position.
  • the shield 5 may be of any suitable material which will provide a. sufficient reduction in temperature in the area of the seed crystal 1C that it will not melt when passed under the heaters 4 and that will reduce the temperature gradient between solid and liquid. In this illustration, involving radiant heaters, aluminum foil has been found to be quite satisfacotry.
  • Relative motion with respect to the sources of heat 4 and the semiconductor material 1 is indicated by the arrow 6.
  • the relative motion may be in any constant direction so long as the successive molten zones 1Dac, separated by single crystal zones 18:: and 13b progress serially away from the region in which the seed crystal 1C is located. Where the seed 1C is drawn through the heating zones the heat control element 5 travels with it and shields the seed from the heat as by breaking up the heat transfer as shown by the break in the radiant rays at points 7.
  • molten region refining operations are carried out in an environment that is free of contaminating impurities and elements that are likely to enter into a chemical reaction with the semiconductor material.
  • the refining operation is usually done in a sealed container, such as for example, a quartz tube labelled element 8.
  • the tube may be evacuated or a neutral gas is either sealed in the tube or is passed over the material 1 as during the refining operation.
  • relative motion indicated by the arrow 6 then will progress with the unrefined germanium material 1A being first traversed by the first molten zone lDa so that a major portion of the impurities contained therein will be retained in the molten zone.
  • the refined region IE1 is permitted to solidify after the zone lDa moves in the direction opposite to the arrow 6.
  • the second molten zone 1Db passes progressively along the semiconductor material permitting the material to solidify in a more refined state.
  • the molten region 1Dc passes progressively along and the single crystal 3 grows from theface 2 of the seed crystal.
  • the radiant heaters 4 may be ellipsoidal reflectors having a 4 inch radius equipped with a one thousand watt bulb positioned at approximately the focus, located about 10 inches from the semiconductor material 1.
  • the rate. of relative motion may be approximately 0.001 inch per second.
  • the approximate width of the molten zone is 0.3 inch.
  • the approximate distance between molten zones is 0.8 inch.
  • a single crystal zone refining device comprising a longitudinally disposed quantity of zone refinable material, a plurality of sources of heat each capable of rendering a discrete portion of said material in a molten condition, each of said sources of heat being longitudinally disposed with respect to the other of said sources of heat so that each molten region in said material associated with a particular source of heat is longitudinally separated from the next adjacent molten region by a region of solidified single crystal material, means for providing relative motion parallel with a longitudinal direction of said material between said sources of heat and said material, a seed of monocrystalline material in contact with the portion of said material first traversed by a molten region and a heat controlling member operable to restrict the application of heat to said seed crystal.
  • an elongated body of semiconductor material means applying heat only to a restricted narrow portion of said body, means for imparting relative motion between the source of said heat and said body, operable to cause a restricted narrow molten zone in said body to traverse the longitudinal axis of said body, a seed crystal in contact with the forward portion of said body in the direction of said relative motion, and shielding means controlling the amount of said heat applied to said seed crystal.
  • a single crystal zone refining apparatus comprising a controlled environment container, means maintaining an environment within said container compatible with the growth of monocrystailine material, a quantity of material longitudinally disposed within said container, a pinrality of radiant heating sources each focused to provide a small discrete molten zone in said material at specific spacings along the longitudinal dimension thereof separated by single crystal solidified semiconductor material, means providing relative motion in the longitudinal direction between said material and the focal points or" said radiant heaters, a seed crystal in contact with said material and the focal points of said radiant heaters, a seed crystal in contact with said material in the forward most portion of said longitudinal dimension in the direction of said relative motion and shield means operable to control heat applied to said seed crystal.
  • a method of single crystal refining comprising the steps of providing a seed crystal in contact with a quantity of longitudinally disposed material, providing a plurality of sources of heat each capable of rendering a discrete portion of said material in a molten condition, providing relative motion between said sources of heat and said material in a direction away. from said seed crystal and viding a seed crystal in contact with one extreme of said longitudinally disposed material, providing a plurality of radiant heaters each focused on a discrete portion of said material rendering said discrete portion molten, providing motion to said molten region in a direction away from said seed crystal and providing shielding means controlling the application of heat to said seed crystal.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
US809957A 1959-04-30 1959-04-30 Single crystal refining Expired - Lifetime US3020132A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
NL112210D NL112210C (US07413550-20080819-C00001.png) 1959-04-30
NL250835D NL250835A (US07413550-20080819-C00001.png) 1959-04-30
US809956A US3036898A (en) 1959-04-30 1959-04-30 Semiconductor zone refining and crystal growth
US809957A US3020132A (en) 1959-04-30 1959-04-30 Single crystal refining
FR817453A FR1263807A (fr) 1959-04-30 1960-02-03 Dispositif pour la fabrication de fils à grand volume apparent
GB14353/60A GB915732A (en) 1959-04-30 1960-04-25 Zone refining apparatus
FR825549A FR1263881A (fr) 1959-04-30 1960-04-28 Procédé d'étirage et de raffinage de cristaux semiconducteurs
DEJ22966A DE1243145B (de) 1959-04-30 1960-04-30 Vorrichtung zum Zonenschmelzen von Kristallen, insbesondere von Halbleiterkristallen
DEJ18050A DE1150357B (de) 1959-04-30 1960-04-30 Vorrichtung zum Reinigen von Kristallen, insbesondere von Halbleitereinkristallen, durch Zonenschmelzen

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Application Number Priority Date Filing Date Title
US809957A US3020132A (en) 1959-04-30 1959-04-30 Single crystal refining

Publications (1)

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US3020132A true US3020132A (en) 1962-02-06

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US809957A Expired - Lifetime US3020132A (en) 1959-04-30 1959-04-30 Single crystal refining

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US (1) US3020132A (US07413550-20080819-C00001.png)
DE (2) DE1150357B (US07413550-20080819-C00001.png)
GB (1) GB915732A (US07413550-20080819-C00001.png)
NL (2) NL250835A (US07413550-20080819-C00001.png)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3250842A (en) * 1963-01-15 1966-05-10 Atomic Energy Commission Electron beam zone refining
US3485613A (en) * 1967-11-06 1969-12-23 Corning Glass Works Method of producing a vitreous body by crucibleless fluid zone treatment
US3622280A (en) * 1967-04-29 1971-11-23 Siemens Ag Adjustable heating device for crucible-free zone melting a crystalline rod
US3651386A (en) * 1970-08-24 1972-03-21 Universal Oil Prod Co Pyropolymeric semiconducting organic-refractory oxide material
US3884642A (en) * 1973-07-23 1975-05-20 Applied Materials Inc Radiantly heated crystal growing furnace
USRE28635E (en) * 1970-08-24 1975-12-02 Pyropolymeric semiconducting organic-refractory oxide material
US3926566A (en) * 1973-05-18 1975-12-16 Bicron Corp Processing alkali metal halide salts for growing into crystals in accordance with stockbarger process
US3986837A (en) * 1973-03-08 1976-10-19 Nikkei Kako Kabushiki Kaisha Method of and apparatus for manufacturing single crystal compound semiconductor

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4828445A (en) * 1982-06-14 1989-05-09 Giannuzzi Louis Single-piece pre-shaped wall anchor

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2739088A (en) * 1951-11-16 1956-03-20 Bell Telephone Labor Inc Process for controlling solute segregation by zone-melting

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL89230C (US07413550-20080819-C00001.png) * 1952-12-17 1900-01-01
AT194444B (de) * 1953-02-26 1958-01-10 Siemens Ag Verfahren und Einrichtung zur Behandlung einer längserstreckten Halbleiterkristallanordnung

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2739088A (en) * 1951-11-16 1956-03-20 Bell Telephone Labor Inc Process for controlling solute segregation by zone-melting

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3250842A (en) * 1963-01-15 1966-05-10 Atomic Energy Commission Electron beam zone refining
US3622280A (en) * 1967-04-29 1971-11-23 Siemens Ag Adjustable heating device for crucible-free zone melting a crystalline rod
US3485613A (en) * 1967-11-06 1969-12-23 Corning Glass Works Method of producing a vitreous body by crucibleless fluid zone treatment
US3651386A (en) * 1970-08-24 1972-03-21 Universal Oil Prod Co Pyropolymeric semiconducting organic-refractory oxide material
USRE28635E (en) * 1970-08-24 1975-12-02 Pyropolymeric semiconducting organic-refractory oxide material
US3986837A (en) * 1973-03-08 1976-10-19 Nikkei Kako Kabushiki Kaisha Method of and apparatus for manufacturing single crystal compound semiconductor
US3926566A (en) * 1973-05-18 1975-12-16 Bicron Corp Processing alkali metal halide salts for growing into crystals in accordance with stockbarger process
US3884642A (en) * 1973-07-23 1975-05-20 Applied Materials Inc Radiantly heated crystal growing furnace

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Publication number Publication date
NL250835A (US07413550-20080819-C00001.png)
DE1150357B (de) 1963-06-20
GB915732A (en) 1963-01-16
DE1243145B (de) 1967-06-29
NL112210C (US07413550-20080819-C00001.png)

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