US3002824A - Method and apparatus for the manufacture of crystalline semiconductors - Google Patents

Method and apparatus for the manufacture of crystalline semiconductors Download PDF

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US3002824A
US3002824A US697046A US69704657A US3002824A US 3002824 A US3002824 A US 3002824A US 697046 A US697046 A US 697046A US 69704657 A US69704657 A US 69704657A US 3002824 A US3002824 A US 3002824A
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rod
radiation
melt
ring
temperature
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Francois Marcel Pieter Alfons
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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
    • C30B15/14—Heating of the melt or the crystallised materials
    • 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
    • C30B13/20—Heating of the molten zone by induction, e.g. hot wire technique
    • 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
    • C30B15/20—Controlling or regulating
    • C30B15/22—Stabilisation or shape controlling of the molten zone near the pulled crystal; Controlling the section of the crystal
    • C30B15/24—Stabilisation or shape controlling of the molten zone near the pulled crystal; Controlling the section of the crystal using mechanical means, e.g. shaping guides
    • 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
    • Y10T117/1032—Seed pulling
    • Y10T117/1036—Seed pulling including solid member shaping means other than seed or product [e.g., EDFG die]
    • 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
    • Y10T117/1032—Seed pulling
    • Y10T117/1068—Seed pulling including heating or cooling details [e.g., shield configuration]
    • 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
    • Y10T117/1084—Apparatus for crystallization from liquid or supercritical state having means for producing a moving solid-liquid-solid zone having details of a stabilizing feature
    • 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

  • the invention relates to methods and apparatus for the manufacture of single crystals from a substance, for example a semi-conductor, such as germanium or silicon, in which by supplying heat from outside and/ or by thermal excitation inside the substance by means of a high frequency electric field, a melt of this substance is produced, from which a single crystal is made to grow in a given direction in the form of a circular-cylindrical rod.
  • this rod may be divided into smaller bodies; for instance in the case of a semiconductive substance, these smaller bodies are used in semi-conductive devices, such as transistors or crystal diodes.
  • tive method is zone-leveling, in which in an elongated boat containing a single crystal at one end and otherwise filled with poly-crystalline material, a narrow liquid zone is moved lengthwise of the boat starting from the single crystal side, and finally the zone-floating process, according to which a narrow liquid zone is moved lengthwise along a vertical rod starting froma mono-crystalline side of the rod onwards.
  • Mono-crystalline rods produced according to these known methods suffer from a comparatively high content of dislocations which, moreover, are unevenly distributed over the cross-sectional area of the rod.
  • this tempering of the grown rod at elevated temperature is efiected by means of a high frequency coil heating an elongated graphite cylinder which surrounds the boat.
  • This coil consists of two parts, namely a part having a small pitch for producing the molten zone and a contiguous part of greater pitch by which the graphite cylinder is locally heated sufficiently to maintain this grown, mono-crystalline rod as a whole at a substantially constant temperature a little below its melting temperature.
  • the present invention has for its object to provide a method in which this problem is solved fundamentally without involving the aforesaid disadvantages by maintaining, in that part of the grown mono-crystalline rod where thermal stresses might involve dislocations, a constant temperature gradient which prevents thermal stresses and concomitant dislocations.
  • the loss of heat during the growing process due to radiation at the surface of that portion of the grown single crystal'rod, which has a high temperature exceeding the softening temperature of the substance is compensated by inward radiation of heat from an external heat radiating member which is arranged symmetrically aroundthe axis of the rod and the geometry and the temperature distribution of which are so chosen as to compensate at least partly, but as completely as is practically feasible, for any heat radiated from any one surface element of said portion having the desired constant temperature gradient.
  • the term softening temperature of a material is to be understood to mean the lowest temperature at which dislocations are still produced by thermal stresses inside this material.
  • the softening temperature of germanium and silicon is approximately 400 C. and 800 C. respectively.
  • the invention particularly applies to the two known methods in which cylinder-symmetrical apparatus are used. For these cases the invention delivers two particular examples of radiation members, of which the geometry is so chosen that the radiation member is to be held ata practically constant temperature.
  • the invention is based on the realisation that in such a circular-cylindrical rod a constant temperature gradient can bemaintained by completely compensating the radiation from the surface at this temperature gradient, that is to say by compensating it in such manner that the resulting heat current through any arbitrary surface element is zero. It further takes advantage of the recognition that at least in a finite portion of the grown, single crystal rod, namely that portion the temperature of which exceeds the softening temperature, substantially complete compensation is obtainable in a simple manner only by inward radiation of heat from a source of thermal energy, for example a ring having a suitable geometry and temperature distribution.
  • a heat radiating member which consists of a ring extending coaxially of the rod and being contiguous with the solidification surface, it accommodating the rod with a little clearance and its outside diameter corresponding to or exceeding at least twice the diameter of the rod, while its side facing the grown single crystal rod is flat and has a constant or substantially constant temperature at least corresponding to the melting temperature of the rod. It is of paramount importance for the radiation ring to approach the rod as closely as practically possible without touching it, since it is the nearby parts of the ring which contribute appreciably to said compensation. From theoretical considerations it has further been found that practically ideal compensation at a given temperature gradient inside the rod is obtainable by choosing a given ratio of the outside diameter and the inside diameter.
  • the effect obtained by the invention is also secured when using a heat radiating member consisting of a radiation ring coaxial with the rod and the inner side of which, at least that part surrounding the solidification surface and a contiguous grown mono-crystalline rod portion having a temperature in excess of the softening temperature, tapers conically in a direction corresponding to the direction of growth of the rod and has a substantially constant temperature corresponding at least to the melting temperature of the rod.
  • a heat radiating member consisting of a radiation ring coaxial with the rod and the inner side of which, at least that part surrounding the solidification surface and a contiguous grown mono-crystalline rod portion having a temperature in excess of the softening temperature, tapers conically in a direction corresponding to the direction of growth of the rod and has a substantially constant temperature corresponding at least to the melting temperature of the rod.
  • the radiation ring is preferably made from conductive material having as high a radiation coefficient as possible. It preferably consists of graphite.
  • FIGS. 1 and 4 represent schematically in cross-section two apparatus according to the invention intended for the floating zone technique.
  • FIGS. 2, 3, 5 and 6 are sectional views of forms of an apparatus according to the invention for pulling up a single crystal rod.
  • FIG. 7 is a graph indicating the etch pit density as a function of the distance from the axis for a rod made by means of an apparatus as shown in FIG. 2, and for a rod produced in known manner without having recourse to a radiation ring.
  • FIG. 1 shows schematically an apparatus according to the invention for use in zone-leveling without a crucible.
  • a vertical, freely arranged elongated rod 1, for example consisting of silicon, is locally surrounded by a disc 2 of graphite, the outside diameter of which is twice to three times as large as the diameter of the rod.
  • the graphite ring 2 is heated by means of a high-frequency field produced by a high-frequency coil 3. Due to thermal radiation from the inner side of the graphite ring 2, a narrow liquid zone 4 is formed and maintained in the rod, which zone is movable lengthwise of the rod, for example by vertical displacement of the graphite ring 2 and the highfrequency coil 3.
  • the thickness of the ring 2 is determined by the amount of heat required for melting the zone.
  • the graphite ring accommodates the rod 1 with a little clearance so that neither the melt nor the rod is touched by the ring. From a mono-crystalline end onwards, for example the top of the rod, the radiation ring 2 is moved downwards and the mono-crystalline rod grows in this direction. As a result of thermal radiation from the flat upper side 5 of the ring 2 into a part of the grown rod, for example within a distance corresponding to the diameter of the rod above the solidification surface, the heat radiated at a constant temperature gradient into this part, can be compensated completely. Since the ring 2 has a rectangular cross-sectional area, the growth may alternatively occur in the opposite direction, so that the flat lower side 6 of the ring fulfills the compensating function.
  • the apparatus according to the invention which is diagrammatically shown in FIG. 2, is suitable for drawing a mono-crystalline rod upwards.
  • a crucible 10 for example consisting of graphite, contains a melt 11 of germanium and is heated by means of a high-frequency electric field produced by the high-frequency coil 3.
  • a single crystal rod 1 having a diameter corresponding, but for a little clearance, to the inside diameter of the ring is drawn upwards.
  • the upper side of the ring acts as a heat-radiation compensating wall.
  • the portion of the rod inside the graphite ring 2 is practically still in the molten state.
  • the radiation disc is preferably less than 5 millimetres thick. Since the crucible wall of graphite shields th high-frequency electric field efiiciently from the radiating ring 4, the latter is substantially heated indirectly, namely by the melt. Hence, the radiation ring has a temperature corresponding to or only slightly exceeding the temperature of the melt. This yields no ideal compensation, it is true, but at least a great improvement upon the known method without using an additional radiation ring. In the absence of the radiation ring, the surface of the melt acts as acompensating heat-radiation member. In practice, this compensation proves to be inadequate due to the low radiation coefficient of the molten material.
  • the temperature of the radiation ring may be further increased by providing the upright walls of the crucible 10 with incisions of such a small width, for example 0.25 mm., as to prevent the melt, owing to its surface tension, from flowing out of the crucible through these incisions. In this case, a relatively larger part of the high frequency field is allowed to penetrate to the radiation disc and to heat it instantly.
  • the temperature of the floating radiation ring may be increased to exceed the melting temperature when using a crucible of insulating material, for example a quartz crucible, in combination with a radiation ring of conductive material, for example a graphite ring.
  • a radiation ring of conductive material for example a graphite ring.
  • the radiation ring is directly heated by means of the high-frequency field, and formation of the melt may be initiated and controlled by the heat radiated from the radiation ring.
  • the two last-mentioned steps according to the invention have a further advantage in that the vertical upstanding wall of the melting crucible is heated only to a comparatively low temperature, so that the amount of radiation reaching the surface of the mono-crystalline rod and interfering with the desired radiation pattern is reduced.
  • a vertical radiation wall for example the conventional high, narrow radiation ring used in zone leveling and the inside diameter of which considerably exceeds the rod diameter, or the crucible wall overtopping the melt upon drawing the rod upwards, yields a radiation pattern greatly different from the desired radiation compensation.
  • FIG. 3 shows diagrammatically an apparatus in which the invention is applied to a known apparatus for drawing mono-crystalline rods upwards.
  • This apparatus permits a mono-crystalline rod to be made having a substantially constant specific resistance in a longitudinal direction.
  • the mono-crystalline rod 1 is lifted from a crucible 15 which floats in the melt 11 of a larger crucible 16 which is connected through an opening 17 with the melt 11 of the larger crucible 16.
  • the liquid levels in both crucibles are the same or substantially the same.
  • the floating crucible 15 comprises a flat edge 18 preferably having the width referred to above, the upper side of which constitutes the compensating radiation surface, while its lower end rests on the melt 11 so that the liquid level inside the crucible extends approximately to the flat edge, the crucible (15, 18) being of such a size, or the pull rate of the mono-crystalline rod being so adjusted that the diameter of the mono-crystalline rod corresponds, but for a little clearance, to the inside diameter of the flat edge of the crucible.
  • FIGS. 4, and 6 show apparatus according to the invention, in which the external heat-radiating member is constituted by a radiation ring co-axial with the rod and the inner side of which, at least the part surrounding the surface of solidification and a contiguous grown monocrystalline rod portion having a temperature exceeding the softening temperature, tapers conically in the sense corresponding to the sense of growth of the rod.
  • the radiation ring is heated to such a high substantially constant temperature that the plan of solidification lies within the conical part of the radiation ring.
  • FIG. 4 shows an apparatus according to the invention, intended for zone melting without using a crucible.
  • the vertical rod 1 is surrounded by a radiation ring 25 having a cross-section in the form of a trapezium, the shorter parallel side 26 of which faces the rod 1.
  • the ring comprises an inner cylindrical part between its two parts extending conically towards the melt.
  • the generatrices of the two conical parts subtend an angle a of approximately 45 with the axis of the rod.
  • the rod On lowering the radiation ring 25 and the high-frequency coil 3 the rod grows mono-crystalline from top to bottom and the upper conical part acts as a compensating heat radiation ring. During the upward movement the rod grows from bottom to top and the lower conical part acts as a compensating heat-radiation ring.
  • a radiation ring floating on the melt is used similarly as in the device shown in FIG. 2.
  • This radiation ring 3t comprises a conical part flaring in the direction of growth of the rod i.e. in the direction of the melt, which part passes over into a cylindrical part.
  • the radiation ring is kept floating so that only a conical part extends above the melt.
  • the device shown in FIG. 6 is analogous to the device shown in FIG. 3, but in FIG. 6 the said upper edge 18 of the crucible 15 shown in FIG. 3 is replaced by a conically tapering inner wall.
  • a conically tapering inner wall Such a device which comprises a crucible 15 Whose inner wall 35 tapers conically at least at its upper edge and which floats on the melt 111 of a larger crucible 16 and is connected therewith through an opening 17 is known per se. According to the invention, however, the crucible 15 is kept floating in the melt so that only a conically tapering inner wall extends above the liquid level 36 of the crucible. In this manner the lifted rod 1 is subject to radiation only from the conical inner Wall.
  • FIG. 7 is a graphical representation of the results obtained by means of the device and the method illustrated in FIG. 2.
  • the density of the etch pits per cm in arbitrary units is plotted vertically. This density is a measure of the dislocation density inside the crystal, while the distance from the axis X-X of the rod, which axis is indicated in broken lines, is plotted horizontally.
  • the curve'A represents the etch pit distribution over the cross-sectional area of a mono-crystalline rod obtained by means of the method and device shown in FIG. 2.
  • the curve B illustrates the etch pit distribution of a mono-crystalline rod pulled up without using a radiation ring. It is obvious that with the mono-crystalline rod obtained when using a method according to the invention the etch pit density is lower and the etch pits are distrib uted more evenly over the cross-sectional area, the etch pit density still increasing considerably only at the edge of the rod. In this connection it is pointed out, however, that the temperature of the floating radiation ring was lower than that required for ideal compensation. In spite thereof the improvement obtained was appreciable.
  • Apparatus for growing, by crystal cylindrical pulling, a single crystal semi-conductive rod comprising a crucible for holding a quantity of molten semi-conductive material, a heating coil surrounding the crucible for adding heat thereto, an annular heat radiator within the crucible and contacting the melt, means for drawing molten material up through the opening in the radiator to cause same to solidify into a rod whose diameter is just slightly less than the diameter of the radiator opening, said radiator having a high radiation coefiicient and a high radiating surface at the melt surface, and means for maintaining said radiation at a temperature at least equal to that of the melt to cause the just-grown rod to receive radiant heat therefrom to compensate for its own heat loss and thus improve the quality of the grown rod.
  • Apparatus for growing a single crystal cylindrical semi-conductive rod comprising a crucible containing semi-conductive material, a high-frequency heating coil surrounding the crucible for melting the semi-conductive material therein, an annular disc-like heat radiator having a circular opening and a relatively high radiation coefficient and having an outwardly extending heat-radiating surface at the melt surface, means for pulling a growing single crystal from the melt up through the annular radiator so that the rod diameter is slightly smaller than the inner diameter of the annular radiator, and means for maintaining said radiator at a temperature at least equal to that of the melt, thereby to radiate heat to the 7 just-grown portion of the rod to compensate for its own :heat loss and thus to improve the quality of the grown od.
  • Apparatus for growing, by crystal pulling, a single crystal semi-conductive rod comprising a large crucible for holding a quantity of molten semi-conductive ma terial, a heating coil surrounding the crucible for adding heat thereto, an annular heat radiator with an inner, outvvardly-tapered radiating surface within the crucible and floating on the melt such that only the tapered surface extends above the melt, and means for drawing molten material up through the opening in the radiator to cause same to solidify into a rod whose diameter is just slightly less than the diameter of the radiator opening; said radiator having a high radiation coefilcient, and means for maintaining said radiator at a temperature at least equal to that of the melt to cause the just-grown rod to receive radiant heat therefrom to compensate for its own heat loss and thus improve the quality of the grown rod.
  • a method for growing a single crystal in the form of a substantially cylindrical rod from a semiconductive melt comprising providing in contact with the melt an apertured annular member whose inner diameter is only slightly greater than the rod diameter to be grown and whose outer diameter is at least twice the said rod diameter and having a high radiation coefficient, contacting the melt through the aperture in the annular member with a single crystal, drawing the single crystal upwards through the apertured annular member so that the grown rod just fills the aperture, and maintaining said annular member at a temperature at least equal to that of the melt thereby radiating heat to the just-grown rod portion contiguous with the molten zone, thereby to improve the quality of the resultant single 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)
  • Mechanical Engineering (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
US697046A 1956-11-28 1957-11-18 Method and apparatus for the manufacture of crystalline semiconductors Expired - Lifetime US3002824A (en)

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US (1) US3002824A (ko)
BE (1) BE562704A (ko)
CH (1) CH397601A (ko)
DE (2) DE1419207A1 (ko)
FR (1) FR1196959A (ko)
GB (1) GB827465A (ko)
NL (1) NL104388C (ko)

Cited By (37)

* 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
US3241925A (en) * 1960-08-19 1966-03-22 Union Carbide Corp Apparatus for growing solid homogeneous compositions
US3249404A (en) * 1963-02-20 1966-05-03 Merck & Co Inc Continuous growth of crystalline materials
US3291650A (en) * 1963-12-23 1966-12-13 Gen Motors Corp Control of crystal size
US3291571A (en) * 1963-12-23 1966-12-13 Gen Motors Corp Crystal growth
DE1235265B (de) * 1961-10-13 1967-03-02 Philips Nv Vorrichtung zum Ziehen von Kristallen aus Schmelzen
US3340016A (en) * 1963-09-26 1967-09-05 Consortium Elektrochem Ind Producing and regulating translatory movement in the manufacture of semiconductor bodies
US3342560A (en) * 1963-10-28 1967-09-19 Siemens Ag Apparatus for pulling semiconductor crystals
US3410665A (en) * 1963-08-17 1968-11-12 Siemens Ag Apparatus for producing striationless bodies of metal and semiconductor substances containing impurities
DE1286510B (de) * 1962-11-23 1969-01-09 Siemens Ag Verfahren zur Herstellung von bandfoermigen, aus Halbleitermaterial bestehenden Einkristallen durch Ziehen aus einer Schmelze
DE1289519B (de) * 1962-11-19 1969-02-20 Siemens Ag Vorrichtung zum Ziehen eines Halbleiterkristalls aus einer Schmelze
US3527574A (en) * 1966-09-27 1970-09-08 Tyco Laboratories Inc Growth of sapphire filaments
US3607115A (en) * 1969-10-29 1971-09-21 Gen Motors Corp Crystal pulling from molten melts including solute introduction means below the seed-melt interface
US3607109A (en) * 1968-01-09 1971-09-21 Emil R Capita Method and means of producing a large diameter single-crystal rod from a polycrystal bar
US3690367A (en) * 1968-07-05 1972-09-12 Anadite Inc Apparatus for the restructuring of metals
US3976536A (en) * 1973-04-18 1976-08-24 Siemens Aktiengesellschaft Method for producing a controlled radial path of resistance in a semiconductor monocrystalline rod
US4000030A (en) * 1975-06-09 1976-12-28 International Business Machines Corporation Method for drawing a monocrystal from a melt formed about a wettable projection
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
US4039283A (en) * 1973-04-18 1977-08-02 Siemens Aktiengesellschaft Apparatus for producing a controlled radial path of resistance in a semiconductor monocrystalline rod
US4090851A (en) * 1976-10-15 1978-05-23 Rca Corporation Si3 N4 Coated crucible and die means for growing single crystalline silicon sheets
US4116642A (en) * 1976-12-15 1978-09-26 Western Electric Company, Inc. Method and apparatus for avoiding undesirable deposits in crystal growing operations
US4167554A (en) * 1974-10-16 1979-09-11 Metals Research Limited Crystallization apparatus having floating die member with tapered aperture
US4196171A (en) * 1977-09-05 1980-04-01 Tokyo Shibaura Denki Kabushiki Kaisha Apparatus for making a single crystal of III-V compound semiconductive material
US4211600A (en) * 1974-12-04 1980-07-08 Metals Research Limited Crystal growth
US4264385A (en) * 1974-10-16 1981-04-28 Colin Fisher Growing of crystals
US4271129A (en) * 1979-03-06 1981-06-02 Rca Corporation Heat radiation deflectors within an EFG crucible
FR2488916A1 (fr) * 1980-08-20 1982-02-26 Us Energy Procede et appareil de tirage d'un ruban monocristallin, en particulier semi-conducteur, d'un bain de matiere fondue
US4497777A (en) * 1981-04-28 1985-02-05 Tokyo Shibaura Denki Kabushiki Kaisha Apparatus for producing monocrystalline silicon
US4750969A (en) * 1985-06-27 1988-06-14 Research Development Corporation Of Japan Method for growing single crystals of dissociative compound semiconductor
US4894206A (en) * 1986-09-22 1990-01-16 Kabushiki Kaisha Toshiba Crystal pulling apparatus
US4938837A (en) * 1985-10-12 1990-07-03 Sumitomo Electric Industries, Ltd. Crucible recovering method and apparatus therefor
US4944925A (en) * 1985-06-10 1990-07-31 Sumitomo Electric Industries, Ltd. Apparatus for producing single crystals
US4944834A (en) * 1985-09-11 1990-07-31 Sumitomo Electric Industries, Ltd. Process of pulling a crystal
US4990179A (en) * 1990-04-23 1991-02-05 Fmc Corporation Process for increasing the life of carbon crucibles in plasma furnaces
US5145550A (en) * 1984-02-21 1992-09-08 Sumitomo Electric Industries, Ltd. Process and apparatus for growing single crystals of III-V compound semiconductor
US5370078A (en) * 1992-12-01 1994-12-06 Wisconsin Alumni Research Foundation Method and apparatus for crystal growth with shape and segregation control
WO2000052233A1 (en) * 1999-03-04 2000-09-08 Solmecs (Israel) Ltd. Apparatus for growing single crystals

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GB754767A (en) * 1953-05-18 1956-08-15 Standard Telephones Cables Ltd Improvements in or relating to methods of crystallizing from melts
US2809136A (en) * 1954-03-10 1957-10-08 Sylvania Electric Prod Apparatus and method of preparing crystals of silicon germanium group
US2855355A (en) * 1945-11-28 1958-10-07 Leo A Ohlinger Jacketed uranium slug
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US2855355A (en) * 1945-11-28 1958-10-07 Leo A Ohlinger Jacketed uranium slug
US2739088A (en) * 1951-11-16 1956-03-20 Bell Telephone Labor Inc Process for controlling solute segregation by zone-melting
US2753280A (en) * 1952-05-01 1956-07-03 Rca Corp Method and apparatus for growing crystalline material
FR1087946A (fr) * 1952-12-17 1955-03-01 Western Electric Co Procédé de production de matières semi-conductrices
US2876147A (en) * 1953-02-14 1959-03-03 Siemens Ag Method of and apparatus for producing semiconductor material
GB754767A (en) * 1953-05-18 1956-08-15 Standard Telephones Cables Ltd Improvements in or relating to methods of crystallizing from melts
US2686212A (en) * 1953-08-03 1954-08-10 Gen Electric Electric heating apparatus
US2809136A (en) * 1954-03-10 1957-10-08 Sylvania Electric Prod Apparatus and method of preparing crystals of silicon germanium group
US2892739A (en) * 1954-10-01 1959-06-30 Honeywell Regulator Co Crystal growing procedure

Cited By (37)

* 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
US3241925A (en) * 1960-08-19 1966-03-22 Union Carbide Corp Apparatus for growing solid homogeneous compositions
DE1235265B (de) * 1961-10-13 1967-03-02 Philips Nv Vorrichtung zum Ziehen von Kristallen aus Schmelzen
DE1289519B (de) * 1962-11-19 1969-02-20 Siemens Ag Vorrichtung zum Ziehen eines Halbleiterkristalls aus einer Schmelze
DE1286510B (de) * 1962-11-23 1969-01-09 Siemens Ag Verfahren zur Herstellung von bandfoermigen, aus Halbleitermaterial bestehenden Einkristallen durch Ziehen aus einer Schmelze
US3249404A (en) * 1963-02-20 1966-05-03 Merck & Co Inc Continuous growth of crystalline materials
US3410665A (en) * 1963-08-17 1968-11-12 Siemens Ag Apparatus for producing striationless bodies of metal and semiconductor substances containing impurities
US3340016A (en) * 1963-09-26 1967-09-05 Consortium Elektrochem Ind Producing and regulating translatory movement in the manufacture of semiconductor bodies
US3342560A (en) * 1963-10-28 1967-09-19 Siemens Ag Apparatus for pulling semiconductor crystals
US3291571A (en) * 1963-12-23 1966-12-13 Gen Motors Corp Crystal growth
US3291650A (en) * 1963-12-23 1966-12-13 Gen Motors Corp Control of crystal size
US3527574A (en) * 1966-09-27 1970-09-08 Tyco Laboratories Inc Growth of sapphire filaments
US3607109A (en) * 1968-01-09 1971-09-21 Emil R Capita Method and means of producing a large diameter single-crystal rod from a polycrystal bar
US3690367A (en) * 1968-07-05 1972-09-12 Anadite Inc Apparatus for the restructuring of metals
US3607115A (en) * 1969-10-29 1971-09-21 Gen Motors Corp Crystal pulling from molten melts including solute introduction means below the seed-melt interface
US4039283A (en) * 1973-04-18 1977-08-02 Siemens Aktiengesellschaft Apparatus for producing a controlled radial path of resistance in a semiconductor monocrystalline rod
US3976536A (en) * 1973-04-18 1976-08-24 Siemens Aktiengesellschaft Method for producing a controlled radial path of resistance in a semiconductor monocrystalline rod
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
US4167554A (en) * 1974-10-16 1979-09-11 Metals Research Limited Crystallization apparatus having floating die member with tapered aperture
US4264385A (en) * 1974-10-16 1981-04-28 Colin Fisher Growing of crystals
US4211600A (en) * 1974-12-04 1980-07-08 Metals Research Limited Crystal growth
US4000030A (en) * 1975-06-09 1976-12-28 International Business Machines Corporation Method for drawing a monocrystal from a melt formed about a wettable projection
US4090851A (en) * 1976-10-15 1978-05-23 Rca Corporation Si3 N4 Coated crucible and die means for growing single crystalline silicon sheets
US4116642A (en) * 1976-12-15 1978-09-26 Western Electric Company, Inc. Method and apparatus for avoiding undesirable deposits in crystal growing operations
US4196171A (en) * 1977-09-05 1980-04-01 Tokyo Shibaura Denki Kabushiki Kaisha Apparatus for making a single crystal of III-V compound semiconductive material
US4271129A (en) * 1979-03-06 1981-06-02 Rca Corporation Heat radiation deflectors within an EFG crucible
FR2488916A1 (fr) * 1980-08-20 1982-02-26 Us Energy Procede et appareil de tirage d'un ruban monocristallin, en particulier semi-conducteur, d'un bain de matiere fondue
US4497777A (en) * 1981-04-28 1985-02-05 Tokyo Shibaura Denki Kabushiki Kaisha Apparatus for producing monocrystalline silicon
US5145550A (en) * 1984-02-21 1992-09-08 Sumitomo Electric Industries, Ltd. Process and apparatus for growing single crystals of III-V compound semiconductor
US4944925A (en) * 1985-06-10 1990-07-31 Sumitomo Electric Industries, Ltd. Apparatus for producing single crystals
US4750969A (en) * 1985-06-27 1988-06-14 Research Development Corporation Of Japan Method for growing single crystals of dissociative compound semiconductor
US4944834A (en) * 1985-09-11 1990-07-31 Sumitomo Electric Industries, Ltd. Process of pulling a crystal
US4938837A (en) * 1985-10-12 1990-07-03 Sumitomo Electric Industries, Ltd. Crucible recovering method and apparatus therefor
US4894206A (en) * 1986-09-22 1990-01-16 Kabushiki Kaisha Toshiba Crystal pulling apparatus
US4990179A (en) * 1990-04-23 1991-02-05 Fmc Corporation Process for increasing the life of carbon crucibles in plasma furnaces
US5370078A (en) * 1992-12-01 1994-12-06 Wisconsin Alumni Research Foundation Method and apparatus for crystal growth with shape and segregation control
WO2000052233A1 (en) * 1999-03-04 2000-09-08 Solmecs (Israel) Ltd. Apparatus for growing single crystals

Also Published As

Publication number Publication date
BE562704A (ko)
NL104388C (ko)
DE1419207A1 (de) 1969-03-27
FR1196959A (fr) 1959-11-27
DE1272900B (de) 1968-07-18
GB827465A (en) 1960-02-03
CH397601A (de) 1965-08-31

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