US20080163815A1 - Device for producing the growth of a semiconductor material - Google Patents

Device for producing the growth of a semiconductor material Download PDF

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Publication number
US20080163815A1
US20080163815A1 US11/972,111 US97211108A US2008163815A1 US 20080163815 A1 US20080163815 A1 US 20080163815A1 US 97211108 A US97211108 A US 97211108A US 2008163815 A1 US2008163815 A1 US 2008163815A1
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Prior art keywords
melt
growth
producing
semiconductor material
seed crystal
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US11/972,111
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English (en)
Inventor
Sylvain Paltrier
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Societe Francaise de Detecteurs Infrarouges SOFRADIR SAS
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Societe Francaise de Detecteurs Infrarouges SOFRADIR SAS
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Assigned to SOCIETE FRANCAISE DE DETECTEURS INFRAROUGES - SOFRADIR reassignment SOCIETE FRANCAISE DE DETECTEURS INFRAROUGES - SOFRADIR ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PALTRIER, SYLVAIN
Publication of US20080163815A1 publication Critical patent/US20080163815A1/en
Priority to US14/465,875 priority Critical patent/US9719187B2/en
Abandoned legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B11/00Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/003Heating or cooling of the melt or the crystallised material
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B11/00Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B11/00Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/002Crucibles or containers for supporting the melt
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B11/00Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/14Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method characterised by the seed, e.g. its crystallographic orientation
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • C30B29/46Sulfur-, selenium- or tellurium-containing compounds
    • C30B29/48AIIBVI compounds wherein A is Zn, Cd or Hg, and B is S, Se or Te
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02367Substrates
    • H01L21/0237Materials
    • H01L21/02373Group 14 semiconducting materials
    • H01L21/02376Carbon, e.g. diamond-like carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02367Substrates
    • H01L21/02428Structure
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02518Deposited layers
    • H01L21/02521Materials
    • H01L21/02551Group 12/16 materials
    • H01L21/02562Tellurides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02612Formation types
    • H01L21/02617Deposition types
    • H01L21/02623Liquid deposition
    • H01L21/02625Liquid deposition using melted materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02612Formation types
    • H01L21/02617Deposition types
    • H01L21/02636Selective deposition, e.g. simultaneous growth of mono- and non-monocrystalline semiconductor materials
    • H01L21/02639Preparation of substrate for selective deposition
    • H01L21/02645Seed materials
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B15/00Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/20Controlling or regulating
    • C30B15/22Stabilisation or shape controlling of the molten zone near the pulled crystal; Controlling the section of the crystal
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10Inorganic compounds or compositions
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S117/00Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
    • Y10S117/911Seed or rod holders
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T117/00Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
    • Y10T117/10Apparatus
    • Y10T117/1024Apparatus for crystallization from liquid or supercritical state

Definitions

  • the invention relates to a device for producing the crystal growth of semiconductor compounds of type II-VI. It relates in particular to the growth of such ternary semiconductor materials having the general formula Cd x Zn 1-x Te, where x can have any value between zero and one.
  • the invention also has an application for the growth of compounds of this family incorporating selenium instead of tellurium, and even quaternary compounds having the formula Cd x Zn 1-x Te y Se 1-y .
  • the present invention applies to the preparation of such semiconductor materials produced in a sealed bulb, that is under vacuum or under controlled atmosphere.
  • the materials thereby obtained are more particularly intended to serve as epitaxial substrates for semiconductor compounds having the generic formula CdHgTe well known for the production of infrared detectors.
  • the materials covered by the invention are also suitable for use for preparing X-ray or gamma ( ⁇ ) ray detectors.
  • the supercooling mechanism alters the crystal yield and, above all, the crystallographic quality of the resulting solid, which is in any case inadequate for a large number of potential applications.
  • the solution it recommends for overcoming this problem essentially resides in the deposition, on the bottom of the crucible receiving the melt, of a layer of solid material surmounted by the melt, and in very accurate and very strict control of the pressure and temperature conditions of the heating furnace in which the sealed bulb containing the said crucible is placed, the temperature gradient being kept lower than 10° C. per centimetre.
  • the conditions for producing the growth of the single crystal are particularly draconian and difficult to industrialize in practice.
  • document JP 7291782 describes a method implementing this general principle. It describes the combination of a single seed crystal of CdTe floating on its growth melt, and initiating the crystallization from the upper surface of the melt.
  • this technique presupposes that the solid CdTe seed crystal floats on its liquid.
  • this requirement can only be met by using a seed crystal having a diameter substantially equal to the diameter of the crucible, thereby raising two particular difficulties:
  • the invention proposes to implement the method of genesis of semiconductor single crystals carried out in a sealed bulb according to the methods described previously, but favouring the nucleation step by using a substance floating on the melt that is both chemically and thermally inert, in order to permit the growth of the solid while supporting the said solid as it grows on the surface of the melt.
  • the invention relates to a device for producing the growth of the semiconductor material from a melt of the said semiconductor placed in a sealed bulb under vacuum or under controlled atmosphere, the said bulb being subjected to a sufficient temperature gradient for first maintaining the melt in the liquid state, then causing its progressive crystallization from the surface towards the bottom.
  • the said device is characterized in that it further comprises an element capable of floating on the surface of the said melt, and equipped with a substantially central bore, intended on the one hand for receiving a seed crystal or for permitting the nucleation leading to the preparation of a seed crystal, and also of supporting the said seed crystal above the melt while maintaining it in contact with the said melt in order to permit the continued crystallization from the said seed crystal by lowering the temperature gradient.
  • a growth seed crystal hence solid, is previously positioned in the central bore, placed so that it is in contact with the melt but without allowing it to be completely or almost completely immersed, as it would naturally do under its own weight.
  • the said seed crystal therefore, as in the preceding case, causes the crystal growth of the semiconductor throughout the mass of the melt.
  • the said floating element is made from a chemically and thermally inert refractory material, selected from the group comprising silica, alumina, silicon carbide, aluminium nitride and carbon in all its forms, but preferably in graphite form.
  • the said element substantially occupies the whole upper surface of the melt, with the exception of the central bore, in order to minimize the effects of the heat radiation inherent in the temperature of the melt, thereby serving to avoid the fusion of the solid being formed.
  • FIG. 1 is a schematic representation of the principle of the invention according to a first embodiment of the invention using a seed crystal.
  • FIG. 2 is a similar view to FIG. 1 , showing the spontaneous solidification of a polycrystalline seed crystal suitable for initializing growth.
  • a first embodiment of the invention is described in relation to FIG. 1 .
  • crucible ( 1 ) made from a refractory material and typically from silica.
  • the diameter of the said crucible is 90 mm for example.
  • the said crucible may be placed in a sealed bulb not shown, or the said bulb may itself act as the crucible. It is positioned in a heating furnace, in order to subject the bulb to a thermal gradient such as shown in the right hand part of the said FIG. 1 .
  • a charge of CdTe is placed in the said crucible ( 1 ), the said charge, when placed in the furnace, and due to the thermal gradient imposed thereby, is in the liquid state, and therefore at a temperature in the present case above 1092° C., the melting point of the compound CdTe.
  • the said graphite cylinder has a thickness of 15 mm. It is provided with a frustoconical bore ( 4 ), whereof the small base is directed downwards and therefore terminates in the melt, and the large base is directed upwards, as may be observed in FIG. 1 .
  • the graphite flows without difficulty on the surface of the CdTe melt, whereof the specific gravity is between 5 and 6.
  • carbon in all its forms is well known for its chemical inertness, its refractory properties, its thermal inertia, and also has the advantage over other materials, such as for example silica, alumina, aluminium nitride or silicon carbide, of being easily machinable, thereby favouring the preparation of the frustoconical bore ( 4 ).
  • a single seed crystal ( 5 ) of CdTe is positioned in the truncated cone thus defined, having sufficient dimensions to be retained by the walls of the bore, and yet allowing it to be flushed with and even in contact with the upper surface of the melt ( 2 ).
  • the core of the invention resides in the maintenance of the seed crystal according to the preceding characteristics, and by all possible means, the truncated cone merely constituting one convenient embodiment.
  • the initial shape of the seed crystal ( 5 ) has accordingly been shown by a dotted line, that is prior to the melting of the charge. Under the action of the melt temperature, the seed crystal is partially melted, until a new solid/liquid interface is defined, positioned at the fusion/solidification isotherm of the compound CdTe, and typically 1092° C.
  • this method for producing the single crystal material is carried out without laborious temperature adjustments owing primarily to the use of the graphite cylinder ( 3 ) and the conformation of its bore ( 4 ), contrary to the prior art, in which the seed crystal floats freely on the melt, the emergent part of the solid being extremely slight due to the very small difference in the solid/liquid densities, the float ( 3 ) thereby serving to avoid the complete fusion of the seed crystal.
  • graphite known for its easy machinability, serves to modify the mechanisms of heat transfers chiefly by conduction, and thereby to adjust the shape and convexity of the solid/liquid interface.
  • Use can be made in particular of pyrolytic graphite, better known as “pyrocarbon” from Le Carbone Lorraine, because of its pronounced thermal anisotropy, suitable for establishing very different heat transfers radially and axially, and thereby promoting single crystal growth.
  • a composite floating support can be considered, for example consisting partly of dense graphite and partly of sheet graphite.
  • Such a composite material is known by the trade name “Papyex”, also from Le Carbone Lorraine.
  • the principle employed remains identical, but with the exception that the seed crystal initiating the nucleation is not joined to the cylinder, but created in situ by lowering the temperature according to a thermal gradient capable of causing the early crystallization of the melt surface.
  • the temperature of the charge is lowered at a gradient such as to cause the crystallization of the melt surface.
  • the first solidified fraction is preferably generated and then maintained at the centre of the melt in the bore prepared in the floating body.
  • a seed crystal is accordingly created, then acting as the initiator of the crystallization that follows, obtained by lowering the temperature of the overall crucible ( 1 ) at a predefined thermal gradient, similar to the one used in the first embodiment described, with natural selection of the favourable crystallization directions and production of a coarse grained, or even single crystal ingot.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
US11/972,111 2007-01-10 2008-01-10 Device for producing the growth of a semiconductor material Abandoned US20080163815A1 (en)

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US14/465,875 US9719187B2 (en) 2007-01-10 2014-08-22 Method for producing the growth of a semiconductor material

Applications Claiming Priority (2)

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FR0752615 2007-01-10
FR0752615A FR2911150B1 (fr) 2007-01-10 2007-01-10 Dispositif pour realiser la croissance d'un materiau semi-conducteur

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4264385A (en) * 1974-10-16 1981-04-28 Colin Fisher Growing of crystals
US20030089300A1 (en) * 2000-10-31 2003-05-15 Ryoji Hoshi Apparatus and method for producing silicon semiconductor single crystal

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4605468A (en) * 1984-07-10 1986-08-12 Hughes Aircraft Company Shaped crystal fiber growth method
JPH01294591A (ja) * 1988-05-20 1989-11-28 Sumitomo Electric Ind Ltd 単結晶の製造装置
US5370078A (en) * 1992-12-01 1994-12-06 Wisconsin Alumni Research Foundation Method and apparatus for crystal growth with shape and segregation control
JPH07291782A (ja) * 1994-04-22 1995-11-07 Japan Energy Corp 化合物半導体単結晶の成長方法
TW538445B (en) * 1998-04-07 2003-06-21 Shinetsu Handotai Kk Silicon seed crystal and method for producing silicon single crystal
JP3119306B1 (ja) * 1999-08-02 2000-12-18 住友電気工業株式会社 結晶成長容器および結晶成長方法
JP3648703B2 (ja) * 2000-01-07 2005-05-18 株式会社日鉱マテリアルズ 化合物半導体単結晶の製造方法
JP4464750B2 (ja) * 2004-07-22 2010-05-19 パナソニック電工株式会社 結晶育成装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4264385A (en) * 1974-10-16 1981-04-28 Colin Fisher Growing of crystals
US20030089300A1 (en) * 2000-10-31 2003-05-15 Ryoji Hoshi Apparatus and method for producing silicon semiconductor single crystal

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Publication number Publication date
EP1944393B1 (fr) 2014-12-24
US20140360427A1 (en) 2014-12-11
FR2911150A1 (fr) 2008-07-11
US9719187B2 (en) 2017-08-01
EP1944393A1 (fr) 2008-07-16
FR2911150B1 (fr) 2010-08-20

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