US3141848A - Process for the doping of silicon - Google Patents

Process for the doping of silicon Download PDF

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Publication number
US3141848A
US3141848A US119547A US11954761A US3141848A US 3141848 A US3141848 A US 3141848A US 119547 A US119547 A US 119547A US 11954761 A US11954761 A US 11954761A US 3141848 A US3141848 A US 3141848A
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Prior art keywords
doping
rod
zone
substances
silicon
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Expired - Lifetime
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US119547A
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English (en)
Inventor
Enk Eduard
Nickl Julius
Silbernagl Heinz
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Wacker Chemie AG
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Wacker Chemie AG
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Priority claimed from DEW28070A external-priority patent/DE1190918B/de
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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
    • C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
    • C30B13/08—Single-crystal growth by zone-melting; Refining by zone-melting adding crystallising materials or reactants forming it in situ to the molten zone
    • C30B13/10—Single-crystal growth by zone-melting; Refining by zone-melting adding crystallising materials or reactants forming it in situ to the molten zone with addition of doping materials
    • C30B13/12—Single-crystal growth by zone-melting; Refining by zone-melting adding crystallising materials or reactants forming it in situ to the molten zone with addition of doping materials in the gaseous or vapour state
    • 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
    • C30B13/08—Single-crystal growth by zone-melting; Refining by zone-melting adding crystallising materials or reactants forming it in situ to the molten zone
    • C30B13/10—Single-crystal growth by zone-melting; Refining by zone-melting adding crystallising materials or reactants forming it in situ to the molten zone with addition of doping materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • 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
    • Y10S118/00—Coating apparatus
    • Y10S118/90—Semiconductor vapor doping
    • 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
    • Y10S252/00—Compositions
    • Y10S252/95—Doping agent source material
    • 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
    • Y10S438/00—Semiconductor device manufacturing: process
    • Y10S438/933—Germanium or silicon or Ge-Si on III-V

Definitions

  • crystalline substances can be doped during crucibleless zone melting in a protective gas by passing a gas stream carrying doping substances at normal or slightly superatmospheric pressure past the molten zone.
  • the gas mixture passes through different temperature zones in which doping substances are already given off.
  • the concentration of the doping substances along the axis of the rod varies.
  • doping as used herein is not limited to doping as it is known in the semiconductor art but includes the incorporation of substances which are optically, mechanically, magnetically or thermally efiective.
  • the doping substances which are supplied laterally to the molten zone or zones distribute themselves uniformly in such zone or zones and are built into the solid phase corresponding to the solid/liquid distribution coeflicient and bestow definite properties to the bodies, such as, electrical, magnetic, optical, mechanical or thermal properties, depending upon the type and concentration of the doping substances employed.
  • FIG. 1 diagrammatically illustrates an embodiment of the process according to the invention
  • FIG. 2 diagrammatically illustrates a modification of the process according to the invention
  • FIG. 3 diagrammatically illustrates another modification of the process according to the invention.
  • FIG. 4 diagrammatically illustrates a manner in which the doping material in solid rod form can be supplied from a plurality of directions
  • FIG. 5 diagrammatically illustrates still another modification of the process according to the invention employing a gaseous doping substance
  • FIG. 6 diagrammatically illustrates the manner in which gaseous doping substances can be metered.
  • FIGS. 7-12 illustrate various nozzle arrangements for supplying doping gases to the molten zone.
  • FIGURE 1 The process according to the invention, for example, can be carried out as illustrated in FIGURE 1 in which a zone 2 of the body to be doped, such as the upright silicon rod 1, is melted and then caused to travel through the length of the rod either upwardly or downwardly.
  • a thin doped silicon rod 5 of a diameter of about 3 mm. is slowly fed horizontally to the molten zone 2 between heating elements 4.
  • the doped "ice rod 5 can also be fed laterally to the molten zone 2 from above.
  • FIGURE 3 diagrammatically illustrates an arrangement for feeding the doping rod 5.
  • the doping rod 5 which is fed from the left is held by clamp 6 which is fastened to a shaftor rod '7 which is driven by rack and pinion 8 and 8'.
  • the advantage of the process resides. in that the con trolled predetermined doping, such as effecting a definite specific electric resistance in the body to be doped, is achieved by the linear movement of the doping rod with the aid of the feeding arrangement. Linear movements today are a solved problem and can be carried out with the greatest exactitude. It is possible with the process according to the invention to use a doped rod of uniform or non-uniform cross-section as the source of the doping substance as it is easy to ascertain the measurements of the rod and to program the advance of the doping rod to correspond to its doping substance content.
  • the doping rod also can be uniformly or non-uniformly doped.
  • the process according to the invention furthermore renders it possible by altering the rate of feed of the doping rod or rods to the molten zone to provide for a certain variation of the specific resistance of the body to be doped, for example, its resistance may be caused to decrease from one end to the other.
  • zones with difierent types of conductivity can be produced in one and the same body by using doping bodies containing oppositely acting doping substances. For example, if a silicon rod or tube is first doped with a boron containing doping rod, p-conductive silicon is produced. If the boron containing doping rod is then replaced by a phosphorus containing doping rod a zone with n-conductivity will then be produced in the silicon rod or tube. As a consequence, bodies with many zones of opposite conductivity types. can be produced.
  • the rods used to supply the doping substances can be of round or angular cross-section and preferably are based upon the same material as that of the bodies to be doped. However, other substances which vaporize or melt and do not disturb the dominating properties of the body to be produced can also be used to supply the doping substances. Silicon rods can, for example, be doped with the aid of silicon rods about 3 mm. in diameter containing doping substances, such as, boron, aluminum, indium, gallium or phosphorus, arsenic and antimony. Analogously, in
  • germanium or boron bodies it is preferable to use germanium or boron rods to supply the doping substances.
  • the doping bodies can also be produced from a material which takes part in the make-up of the body to be produced and remains therein.
  • it may be an alloying component or an element which forms a compound with the substance of the rod to be doped.
  • a boron rod containing phosphorus can be employed to dope a silicon rod whereby phosphorus containing borosilicides are produced.
  • the process is also suited for the production of intermetallic compounds, such as the III/V-group element, II/VI- group element and V/IV-group element compounds.
  • the doping bodies can contain the active doping substances in homogeneously or heterogeneously distributed form, for example, they can be in the form of occlusions in solid bodies, or in the form of solid solutions or as dissolved elements or compounds.
  • a further advantage of the process according to the invention is that it is not bound to any particular type of heating employed to produce the travelling molten zone. It is suited equally well when electric high frequency heating, electron or ion bombardment, a plasma burner, an electron torch or radiated heat is employed for such heating.
  • the process furthermore is not limited to the use of any particular range of pressures at which the zone melting is effected as it can be carried out at subatmospheric, atmospheric or superatmospheric pressures.
  • FIGURE 5 diagrammatically shows an apparatus suitable for carrying out the process according to the invention with gaseous doping substances.
  • 9 represents a recipient such as commonly used for zone refining.
  • Rod 1 is first zone refined therein about 5 times either upwardly or downwardly using a high frequency coil 4 as source of heat without addition of the doping gas.
  • the doping gas is supplied to the molten zone through conduit 10 during the entire travel of the molten zone.
  • FIGURE 6 diagrammatically illustrates the manner in which the doping gas is metered.
  • the gas flows from pressure bottle 11 over a pressure reducer 1.2 of known construction and valve 13 into measuring chamber 14 provided with manometer 15. Valves 16 and 17 remain closed and fine regulating valve 1% is opened.
  • FIGURES 7-12 illustrate various arrangements for nozzles for supplying the doping gas to the molten zone.
  • nozzle 19 is arranged perpendicularly to the axis of rod 1 and nozzle 20 is arranged at a downwardly directed angle.
  • nozzle 19 is arranged between two heating coils 4 and inFIGURE 9 the double outlet nozzle 23 is arranged to supply the doping gas to the molten zone symmetrically above or below the heating coil.
  • FIG- URE 11 shows an arrangement in which three nozzles 22 are arranged symmetrically around the rod.
  • the nozzle 24 is projected through the high frequency heating coil 41 to provide a completely symmetrical incidence of the gas stream on the molten zone.
  • the distance of the nozzle outlet from the surface is adapted to pressures which are operated at.
  • Volatile or vaporized organic or inorganic compounds such as, for example, alkyl compounds, aryl compounds, hydrides, halides, oxides, sulfides, selenides and elements either singly or in a mixture are suited as doping substances. They can be supplied to the molten zone either in undiluted form or with the aid of an inert propellant gas.
  • silicon can be doped using boron hydrides, boron halides, phosphorus vapor, phosphine or phosphorus halides as the doping substances.
  • the molten zones during the process according to the invention may be heated by high frequency electron heating, electron bombardment, plasma burners, radiated heat or focused radiation using stationary or moving heating elements.
  • the doping gas can be supplied directly to the fuel gas.
  • germanium rods can be alternately doped with boron hydride and phosphine so that zones with opposite types of conductivity are obtained.
  • the simultaneous supply of oppositely acting doping substances renders it possible to provide zones in which the doping substances are partially or completely compensated.
  • the doping gas or rod need not necessarily be directed against a molten zone which encompasses the entire crosssection of the rod.
  • a very good distribution of the doping substances over the entire cross-section of the rod is achieved in this way.
  • the process according to the invention renders it possible to provide for doping over a wide range of resistances in nand pconductive material, for example, in the case of silicon of about l0 -10 ohm cm. and carrier lives of 10 to several microseconds.
  • the process according to the invention can also be applied to zone melting in crucibles.
  • Example 1 A polycrystalline silicon rod (diam. 15.0-17.3 mm., length 300 mm.) vertically arranged was zone floated in vacuum from 10- to l() mm. Hg. The molten zone was caused to travel 8 times upwardly through the rod with a velocity of 2 mm./min. After the 8th zone passage the rod had a final length of 250 mm. and a diameter of 16.0 mm. This rod was doped in the 9th zone passage by supplying a thin silicon rod (diam. 2010.05 mm, length 350 mm.) to the molten zone. The doping rod had a boron-content corresponding to a resistivity of 7.8 ohm cm. The rate of feed and the velocity of the molten zone in the thick rod was 2 mm./ min.
  • the wanted resistivity of the doped rod should be 500 ohm cm. It was empirically known that the thick rod had an electrical resistivity of about 8000 ohm cm. after the 8th zone passage. The achieved resistivity over alength of 250 mm. was 470112 ohm cm..
  • Example 2 An aluminum rod (diam. 5 mm., length 200 mm.) was vertically arranged zone refined. The velocity of the molten zone was 1.5 mm./min. To this molten zone an antimony rod (2 mm. diam.) was supplied continuously. The rate of supplying was so that the melt had the composition of AlSb. After that 2 further zone passages were carried out in order to make the material monocrystalline.
  • a process for the controlled doping of silicon during zone melting thereof which comprises causing at least 6 one molten zone to travel axially through an elongated vertically arranged body of silicon and supplying a silicon rod, which contains the doping material laterally to said travelling molten zone at a predetermined controlled 5 rate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
  • Silicon Compounds (AREA)
US119547A 1960-06-24 1961-06-26 Process for the doping of silicon Expired - Lifetime US3141848A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEW28070A DE1190918B (de) 1960-06-24 1960-06-24 Verfahren zur gezielten Dotierung von stabfoermigen Koerpern waehrend des Zonenschmelzens

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3311510A (en) * 1964-03-16 1967-03-28 Mandelkorn Joseph Method of making a silicon semiconductor device
US3477959A (en) * 1967-04-24 1969-11-11 Northern Electric Co Method and apparatus for producing doped,monocrystalline semiconductor materials
US3804682A (en) * 1971-08-26 1974-04-16 Siemens Ag Method for controlled doping of semiconductor crystals
US3858549A (en) * 1973-08-15 1975-01-07 Siemens Ag Apparatus for controlled doping of semiconductor crystals
US3908586A (en) * 1973-05-28 1975-09-30 Siemens Ag Apparatus for doping semiconductor rods during floating zone melt processing thereof
US3976536A (en) * 1973-04-18 1976-08-24 Siemens Aktiengesellschaft Method for producing a controlled radial path of resistance in a semiconductor monocrystalline rod
US4210486A (en) * 1976-05-25 1980-07-01 Wacker-Chemitronic Gesellschaft Fur Elektronik-Grundstoffe Mbh Process for determining the effective doping agent content of hydrogen for the production of semiconductors
US4229298A (en) * 1979-02-05 1980-10-21 The Western States Machine Company Method and apparatus for determining the thickness of a charge wall formed in a centrifugal basket
US4270972A (en) * 1980-03-31 1981-06-02 Rockwell International Corporation Method for controlled doping semiconductor material with highly volatile dopant
US4556448A (en) * 1983-10-19 1985-12-03 International Business Machines Corporation Method for controlled doping of silicon crystals by improved float zone technique
JP2012148949A (ja) * 2010-12-28 2012-08-09 Siltronic Ag シリコン単結晶の製造方法、シリコン単結晶、およびウエハ

Citations (3)

* 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
US2964396A (en) * 1954-05-24 1960-12-13 Siemens Ag Producing semiconductor substances of highest purity
US2970111A (en) * 1958-09-20 1961-01-31 Siemens Ag Method of producing a rod of lowohmic semiconductor material

Patent Citations (3)

* 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
US2964396A (en) * 1954-05-24 1960-12-13 Siemens Ag Producing semiconductor substances of highest purity
US2970111A (en) * 1958-09-20 1961-01-31 Siemens Ag Method of producing a rod of lowohmic semiconductor material

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3311510A (en) * 1964-03-16 1967-03-28 Mandelkorn Joseph Method of making a silicon semiconductor device
US3477959A (en) * 1967-04-24 1969-11-11 Northern Electric Co Method and apparatus for producing doped,monocrystalline semiconductor materials
US3804682A (en) * 1971-08-26 1974-04-16 Siemens Ag Method for controlled doping of semiconductor crystals
US3976536A (en) * 1973-04-18 1976-08-24 Siemens Aktiengesellschaft Method for producing a controlled radial path of resistance in a semiconductor monocrystalline rod
US3908586A (en) * 1973-05-28 1975-09-30 Siemens Ag Apparatus for doping semiconductor rods during floating zone melt processing thereof
US3858549A (en) * 1973-08-15 1975-01-07 Siemens Ag Apparatus for controlled doping of semiconductor crystals
US4210486A (en) * 1976-05-25 1980-07-01 Wacker-Chemitronic Gesellschaft Fur Elektronik-Grundstoffe Mbh Process for determining the effective doping agent content of hydrogen for the production of semiconductors
US4229298A (en) * 1979-02-05 1980-10-21 The Western States Machine Company Method and apparatus for determining the thickness of a charge wall formed in a centrifugal basket
US4270972A (en) * 1980-03-31 1981-06-02 Rockwell International Corporation Method for controlled doping semiconductor material with highly volatile dopant
US4556448A (en) * 1983-10-19 1985-12-03 International Business Machines Corporation Method for controlled doping of silicon crystals by improved float zone technique
JP2012148949A (ja) * 2010-12-28 2012-08-09 Siltronic Ag シリコン単結晶の製造方法、シリコン単結晶、およびウエハ
US20130277809A1 (en) * 2010-12-28 2013-10-24 Siltronic Ag Method of manufacturing silicon single crystal, silicon single crystal, and wafer
US8961685B2 (en) * 2010-12-28 2015-02-24 Siltronic Ag Method of manufacturing silicon single crystal, silicon single crystal, and wafer

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NL266156A (pt)
BE605268A (fr) 1961-12-22
GB995087A (en) 1965-06-16

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