US3597171A - Method of crystallization using solvent removal by reaction - Google Patents

Method of crystallization using solvent removal by reaction Download PDF

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Publication number
US3597171A
US3597171A US676511A US3597171DA US3597171A US 3597171 A US3597171 A US 3597171A US 676511 A US676511 A US 676511A US 3597171D A US3597171D A US 3597171DA US 3597171 A US3597171 A US 3597171A
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United States
Prior art keywords
solvent
solution
seed crystal
semiconductor material
silicon
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Expired - Lifetime
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US676511A
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English (en)
Inventor
Wilhelmus Francisc Knippenberg
Gerrit Verspui
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US Philips Corp
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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
    • C30B17/00—Single-crystal growth onto a seed which remains in the melt during growth, e.g. Nacken-Kyropoulos method
    • 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
    • C30B9/00—Single-crystal growth from melt solutions using molten solvents

Definitions

  • This invention relates to the manufacture of crystals intended more particularly for semiconductor devices.
  • semiconductor crystals may be obtained by bringing a seed crystal into contact with a melt of the semiconductor material and maintaining a temperature gradient in the junction layer so that the seed crystal grows.
  • this method can be used only with materials, such as silicon and germanium, which can be melted at acceptable temperatures.
  • silicon carbide can grow on a seed crystal from a molten saturated solution in chromium at an acceptable temperature.
  • This substance is usable as a solvent, since the silicon carbide is satisfactorily soluble in it and this solvent is not absorbed by the crystal to a troublesome extent.
  • This method has been carried out at atmospheric pressure in an inert gas at a temperature slightly above the melting point of the solution, namely approximately 1800 C. As a result of the small temperature difference between the seed crystal and the solution the growing rate of the crystal was low to a troublesome extent.
  • the solvent must then have not only an acceptable solubility of the semiconductor material and not be absorbed by the crystal to a troublesome extent, but also have so high a vapour pressure at the melting temperature that sufiiciently rapid evaporation of the solvent and a rapid crystal growth, as the case may be at reduced pressure, take place.
  • An object of the invention is to mitigate this disadvantage.
  • the present invention underlies recognition of the fact that the state of oversaturation can be obtained in a simple manner by chemical means instead of by physical removal of solvent by evapoartion, possibly at reduced pressure.
  • the invention relates to a method of manufacturing crystals, e.g. crystals for semiconductor devices, in which a seed crystal is brought into contact with a molten saturated solution of a semiconductor material so that the seed crystal grows, and it is characterized in that a gas is supplied to the atmosphere above the solution which gas reacts with the solvent at the temperature of the melt, thus forming a volatile compound so that solvent is extracted from the surface layer and a state of oversaturation is caused in this layer.
  • a gas is supplied to the atmosphere above the solution which gas reacts with the solvent at the temperature of the melt, thus forming a volatile compound so that solvent is extracted from the surface layer and a state of oversaturation is caused in this layer.
  • This method of removing solvent has a less limiting influence on the choice of the solvent or at least an influence which is limiting in another sense than in the case when the said removal is to take place by evaporation at reumbled pressure.
  • the majority of substances which can be used as solvents such as gallium with gallium phosphide, silicon with silicon carbide and tin With silicon, exhibit a low vapour pressure at their melting point.
  • Chromium which can be used as a solvent for silicon carbide, is a favourable exception in this respect.
  • many of the usable solvents at their melting temperatures readily form volatile compounds with gaseous reagents, such as oxygen, sulphur and halogen, so that solvent may rapidly be extracted from the solution.
  • EXAMPLE 1 As shown in the drawing, a seed crystal 1 of gallium phosphide is laid on the surface of a saturated solution 2 consisting of 4 mol percent of gallium phosphide in gallium, which solution is contained in a graphite vessel 3 placed in a quartz tube 4 and maintained in a molten state in argon of atmospheric pressure at a temperature of 1050 C. by means of an oven 5.
  • a chlorine flow of 50 cm. per minute is passed through the quartz tube 4, causing solvent (gallium) to be extracted from the melt while forming volatile gallium chloride, so that oversaturation occurs in the surface layer and the gallium phosphide seed crystal grows at a rate of more than 30p. per hour.
  • the method according to the invention can also be carried out in such manner that the seed crystal is fixed in position relative to the graphite crucible, the seed crystal being able to grow due to the solvent disappearing and the level of the liquid in the crucible falling correspondingly.
  • EXAMPLE 2 By means of a similar device as has been described in Example 1, a solution of 5 at. percent of silicon in tin in a quartz vessel is maintained in the molten state at 900 C.
  • a method of growing crystals for use in semiconductor devices comprising the steps of forming a molten saturated solution of a semiconductor material in a solvent,
  • the semiconductor material is selected from the group consisting of silicon, silicon carbide and gallium phosphide.
  • gaseous reagent is oxygen, sulfur or a halogen.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
US676511A 1966-10-22 1967-10-19 Method of crystallization using solvent removal by reaction Expired - Lifetime US3597171A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL6614999A NL6614999A (enrdf_load_stackoverflow) 1966-10-22 1966-10-22

Publications (1)

Publication Number Publication Date
US3597171A true US3597171A (en) 1971-08-03

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Family Applications (1)

Application Number Title Priority Date Filing Date
US676511A Expired - Lifetime US3597171A (en) 1966-10-22 1967-10-19 Method of crystallization using solvent removal by reaction

Country Status (9)

Country Link
US (1) US3597171A (enrdf_load_stackoverflow)
AT (1) AT270754B (enrdf_load_stackoverflow)
BE (1) BE705462A (enrdf_load_stackoverflow)
CH (1) CH494065A (enrdf_load_stackoverflow)
DE (1) DE1619987B2 (enrdf_load_stackoverflow)
DK (1) DK115390B (enrdf_load_stackoverflow)
GB (1) GB1165037A (enrdf_load_stackoverflow)
NL (1) NL6614999A (enrdf_load_stackoverflow)
SE (1) SE309966B (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996891A (en) * 1974-03-01 1976-12-14 Sony Corporation Liquid phase epitaxial growth apparatus wherein contacted wafer floats
US4415545A (en) * 1980-12-15 1983-11-15 Monkowski Joseph R Solid film growth via preferential etching of liquid solutions
US5544616A (en) * 1992-05-13 1996-08-13 Midwest Research Institute Crystallization from high temperature solutions of Si in Cu/Al solvent

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996891A (en) * 1974-03-01 1976-12-14 Sony Corporation Liquid phase epitaxial growth apparatus wherein contacted wafer floats
US4415545A (en) * 1980-12-15 1983-11-15 Monkowski Joseph R Solid film growth via preferential etching of liquid solutions
US5544616A (en) * 1992-05-13 1996-08-13 Midwest Research Institute Crystallization from high temperature solutions of Si in Cu/Al solvent

Also Published As

Publication number Publication date
SE309966B (enrdf_load_stackoverflow) 1969-04-14
DK115390B (da) 1969-10-06
GB1165037A (en) 1969-09-24
AT270754B (de) 1969-05-12
BE705462A (enrdf_load_stackoverflow) 1968-04-22
DE1619987A1 (de) 1970-03-26
CH494065A (de) 1970-07-31
DE1619987B2 (de) 1977-01-20
NL6614999A (enrdf_load_stackoverflow) 1968-04-23

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