US3619131A - Method of producing stoichiometric mg-al spinel crystals for integrated circuits - Google Patents

Method of producing stoichiometric mg-al spinel crystals for integrated circuits Download PDF

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Publication number
US3619131A
US3619131A US824734A US3619131DA US3619131A US 3619131 A US3619131 A US 3619131A US 824734 A US824734 A US 824734A US 3619131D A US3619131D A US 3619131DA US 3619131 A US3619131 A US 3619131A
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spinel
crystal
powder
mixing ratio
stoichiometric composition
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US824734A
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English (en)
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Josef Grabmaier
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Siemens AG
Siemens Corp
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Siemens 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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/04—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt
    • C30B11/08—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt every component of the crystal composition being added during the crystallisation
    • C30B11/10—Solid or liquid components, e.g. Verneuil method
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass

Definitions

  • METHOD OF PRODUCING STOICHIOMETRIC MG'AL SHNEL CRYSTALS FOR NTEGRATED ABSTRACT A method of producing Mg-Al spinel crystals of CIRQUITS a stoichiometric composition free from precipitation and ten- 7 Clamms Drawmg Flgs' sion, The invention is characterized in that the carrier crystal [52] U.S. Cl 23/52, is an alumina-rich spinel crystal.
  • the crystal growing thereon 23/30l, 23/304, 23/305, 252/632, 252/635, is produced according to its length by changing the provided 252/520, 252/52l mixing ratio of Mg0/Al 0; to a stoichiometric composition of [51] lnt.Cl B0lj l7/24, the desired spinel crystal. During the growth process, slight amounts of'l'iO are added to the spinel powder supplied.
  • monocrystalline spinel can be industrially produced at a mixing ratio only of MgO/Al of 1:2 to 1:4. These spinel which are rich in alumina are strongly tensioned. After cooling in the Verneuil furnace, they are in a state of preprecipation. During a subsequent heat processing which is necessary during annealing and epitactic coating, this preprecipation via a metastable intennediate structure leads to final precipitations of A1 0 These final precipitations occur mainly at the surface and may therefore cause, in the grown semiconductor layer, stability failures, twin formations or even a polycrystalline degenerated growth. These A1 0,, seeds prefer to form inside the crystal at the optically visible places and produce, thereby, an additional tension in the substrate discs.
  • the present invention relates to a method of producing spinel crystals of stoichiometric composition, free of precipitation and tension. more particularly of substrate wafers, to be used in the production of epitaxial layers comprised of semiconductor material, according to the so-called Verneuil method, whereby finely distributed Mg-Al spinel powder is contacted with the heated or molten dome of a carrier crystal caused to cool and crystallize upon the dome and removing the carrier crystal from the heated zone, according to the solidification speed.
  • alumina-rich spinel crystal as a carrier crystal.
  • the crystal grown upon the latter is produced along its length, by changing the mixing ratio of MgO/Al 0; to a stoichiometric combination of the desired spinel crystal, whereby slight additions of Ti0 are added during the growth process to the spinel powder provided.
  • the method of the invention affords the opportunity to produce by mechanical or thermal processes, stable Mg-Al spinel which, because of their highly insulating properties, can be used as substrate bases for the production of epitaxial semiconductor semiconductor materials.
  • a further development of the invention is to use a Mg-Al spinel crystal, composed approximately of Mg0/Al 0 at a ratio of l:3.l as a carrier crystal.
  • the last stage of the growth process then corresponds to the stoichiometric composition of the desired spinel crystal.
  • the section of the grown spinel crystal can be separated from the remaining spinel crystal, including the carrier crystal, following the growth process and can be used directly as a substrate material for epitactic growth processes.
  • the original crystal seed can be used again as a carrier crystal seed for a new production process, after having been separated from the pulled crystal.
  • the method of the present invention is particularly well suited for the production of spinel crystals which are used as substrates for epitactic precipitation of semiconductor materials, particularly of silicon.
  • the integrated circuits produced in these silicon layers are characterized by particularly stable and good electrical characteristics.
  • FIG. 1 shows a crystal produced according to the invention
  • FIGS. 2 and 3 show apparatus for producing such crystal.
  • FIG. I shows an Mg-AI spinel crystal, produced according to the method of the present invention.
  • Region 30 represents an alumina-rich MgAI crystal of composition I23.
  • l used as both a carrier crystal and as the first layer, precipitated thereon which has the same composition.
  • Region 31 is precipitated upon region 30 by using a spinel powder with a composition of l:2.5.
  • Region 32 of the grown crystal corresponds to a powder composition of l:l.7 and region 33 represents the stoichiometric composition of Mg0/Al,0 at a ratio of 1:1.
  • FIG. 2 schematically illustrates a Vemeuil apparatus which is also used for other crystal growth processes, such as growing synthetic rubies.
  • the funnel 1 holds the vibrating box 2 containing the original material 6, provided for the particular section to be produced and comprised, for example of a fine grained Mg-Al oxide powder of an initial composition ratio 1:3.l, followed by 112.5, then 121.7 and finally lzl.
  • the particle sizes are smaller than 70 pm.
  • the material is obtained by heating for approximately 2 hours in a quartz boat, ammoniaaluminum-alum and Mg-Al sulfate, at l,200 C.
  • a metal sieve 3 (mesh size around pm.) is at the bottom of the vibrating box 2.
  • the sieve is clamped on a ring (not shown), which can be screwed upon the vibrating box 2.
  • a hammer 4 is mounted above the funnel l and is operated by a cam 5, driven by a motor. The hammer knocks against the vibrating box 2 filled with oxide powder 6, 60 to 120 times per minute. The filler neck for the respective powder mixture is seen at 28.
  • a burner 7 is installed below the funnel 1. Oxygen, which flows in at arrow 8, is supplied to funnel I while hydrogen, flowing in at arrow 9, is delivered directly to the burner 7, through bores 20 which are also present in the burner pipe. The burner 7 protrudes somewhat with its mouth I7, into a cylindrical furnace 10, encased in an aluminum sheet 11.
  • the furnace is approximately 250 mm. high, with an outer diameter of approximately 250 mm. and an inner diameter of 40 mm. and is sealed on the top with a cover plate 21 and on the bottom with plate 22 of aluminum.
  • the furnace 10 has an observation hole 13, through which the processes going on inside can be observed.
  • the furnace is lined with a casing 12 of fire-resistant ceramic adjusted to the diameter of the furnace.
  • the space between the furnace jacket and the casing is filled in with loose sintered degussit granules or with a firebrick mass 23 with good heat insulation and a thickness of mm.
  • the crystal holder 14 (a small rod or pipe of sintered alumina, degussit or spinel crystal) extends from below into the furnace and is mounted upon the spindle of a gear block which is movable in the perpendicular direction.
  • the gear block serves for removing the grown crystal, and is either hand or motor operated.
  • a carrier seed crystal 30 comprised of an alumina-rich spinel (113.1) is mounted upon the crystal holder 14 and heated by the oxyhydrogen flame.
  • Oxide powder 6, from the vibrating box 2 is delivered first at a composition of 1:13.! through the shacking funnel 18, which is additionally installed into funnel 1 to ensure control of a uniform powder supply to the oxyhydrogen flame and melted.
  • Shacking funnel 18 is also sealed by a metal sieve l9 l60 um. mesh width).
  • the first section, also indicated as 30 in HO. 1, of the spinel rod 16 is obtained at approximately 1,950 C.
  • the spinel is then permitted to continue its growth, if possible with a constant flame and a uniform powder supply, but with an alternating composition, until of desired length.
  • the latter is lowered in accordance with its growth increase, and with the aid of a gear 15, at a pulling velocity of about 5 mm./hr.
  • the powder supply is interrupted and the crystal holder 14, together with the grown crystal 16, comprising the four zones 30, 31, 32, 33, is removed from the heating zone of the Verneuil furnace, with the aid of the drive, either after the oxyhydrogen flame has been turned off or while the flame is burning.
  • the transport and the composition of the reaction gas was effected according to known methods and based on the growth of synthetic rubies.
  • the refilling of the powder with small alumina contents, into the vibrating box 2 is effected by means of a device which is shown in the upper portion of H6. 3.
  • the powder falls from the storage filling funnel into the filler tube 26.
  • clamp 24 is closed and clamp 27 opened, the powder to be refilled arrives, via the tiller neck 28 into the vibrating box 2.
  • the individual stages can be grown, with the aid of the aforedescribed refilling device, without any difficulty and without having to extinguish the flame.
  • the powder is changed, only the melting temperature which changes slightly according to the composition of the powder, has to be considered.
  • the melting temperature of the spinel powder rises somewhat with a stoichiometric composition.
  • the same reference numerals as in FIG. 2 apply to the remaining portions of FIG. 3.
  • a method of producing Mg-Al crystals, of a stoichiometric composition, and free from precipitation and tension, more particularly spinel crystals which comprises bringing divided Mg-Al spinel powder into contact with a heated or molten dome of a carrier crystal, and permitting the powder to cool and crystallize on said dome, moving the carrier crystal out of the heating zone in accordance with the melting speed of said powder, using as the carrier crystal an alumina-rich spinel crystal, and changing the compositions of the crystal growing in accordance with its length by changing provided mixing ratio of MgO/Al 0 to a stoichiometric composition of the desired spinel crystal and adding slight amounts of Ti0 spinel powder supplied during the growth process.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
US824734A 1968-05-06 1969-05-06 Method of producing stoichiometric mg-al spinel crystals for integrated circuits Expired - Lifetime US3619131A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19681767394 DE1767394A1 (de) 1968-05-06 1968-05-06 Verfahren zum Herstellen von Mg-Al-Spinellkristallen mit stoechiometrischer Zusammensetzung fuer integrierte Schaltungen

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US (1) US3619131A (de)
AT (1) AT287652B (de)
CH (1) CH519932A (de)
DE (1) DE1767394A1 (de)
FR (1) FR1598617A (de)
GB (1) GB1220311A (de)
NL (1) NL6906593A (de)
SE (1) SE345395B (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3883313A (en) * 1972-12-14 1975-05-13 Rca Corp Modified czochralski-grown magnesium aluminate spinel and method of making same
US3960503A (en) * 1974-12-27 1976-06-01 Corning Glass Works Particulate material feeder for high temperature vacuum system
US4186046A (en) * 1976-09-29 1980-01-29 The United States Of America As Represented By The Secretary Of The Army Growing doped single crystal ceramic materials
US5002742A (en) * 1983-05-16 1991-03-26 W. R. Grace & Co.-Conn. Inorganic oxide sorbents for sulfur oxides
US5449389A (en) * 1989-08-25 1995-09-12 Mitsubishi Materials Corporation Process for production of fine α-alumina powder
US7648933B2 (en) 2006-01-13 2010-01-19 Dynamic Abrasives Llc Composition comprising spinel crystals, glass, and calcium iron silicate
CN103014855A (zh) * 2012-12-25 2013-04-03 福建鑫磊晶体有限公司 一种用γ-Al2O3制备α-Al2O3单晶体的制备方法及其设备
EP2669410A1 (de) * 2012-05-31 2013-12-04 Innotech Holding GmbH Verfahren zur Kristallzüchtung durch ein Flammenschmelzen

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4792377A (en) * 1987-02-09 1988-12-20 The Regents Of The University Of California Flux growth of sodium beta" alumina

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3226193A (en) * 1962-06-21 1965-12-28 Union Carbide Corp Method for growing crystals
US3457033A (en) * 1965-12-17 1969-07-22 Gen Electric Process for producing magnesiaalumina spinel whiskers
US3472615A (en) * 1967-08-24 1969-10-14 Rca Corp Growing monocrystalline stoichiometric magnesium aluminate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3226193A (en) * 1962-06-21 1965-12-28 Union Carbide Corp Method for growing crystals
US3457033A (en) * 1965-12-17 1969-07-22 Gen Electric Process for producing magnesiaalumina spinel whiskers
US3472615A (en) * 1967-08-24 1969-10-14 Rca Corp Growing monocrystalline stoichiometric magnesium aluminate

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3883313A (en) * 1972-12-14 1975-05-13 Rca Corp Modified czochralski-grown magnesium aluminate spinel and method of making same
US3960503A (en) * 1974-12-27 1976-06-01 Corning Glass Works Particulate material feeder for high temperature vacuum system
US4186046A (en) * 1976-09-29 1980-01-29 The United States Of America As Represented By The Secretary Of The Army Growing doped single crystal ceramic materials
US5002742A (en) * 1983-05-16 1991-03-26 W. R. Grace & Co.-Conn. Inorganic oxide sorbents for sulfur oxides
US5449389A (en) * 1989-08-25 1995-09-12 Mitsubishi Materials Corporation Process for production of fine α-alumina powder
US7648933B2 (en) 2006-01-13 2010-01-19 Dynamic Abrasives Llc Composition comprising spinel crystals, glass, and calcium iron silicate
EP2669410A1 (de) * 2012-05-31 2013-12-04 Innotech Holding GmbH Verfahren zur Kristallzüchtung durch ein Flammenschmelzen
CN103014855A (zh) * 2012-12-25 2013-04-03 福建鑫磊晶体有限公司 一种用γ-Al2O3制备α-Al2O3单晶体的制备方法及其设备

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Publication number Publication date
CH519932A (de) 1972-03-15
GB1220311A (en) 1971-01-27
FR1598617A (de) 1970-07-06
NL6906593A (de) 1969-11-10
AT287652B (de) 1971-02-10
DE1767394A1 (de) 1971-08-26
SE345395B (de) 1972-05-29

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