US3341376A - Method of producing crystalline semiconductor material on a dendritic substrate - Google Patents

Method of producing crystalline semiconductor material on a dendritic substrate Download PDF

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US3341376A
US3341376A US523486A US52348665A US3341376A US 3341376 A US3341376 A US 3341376A US 523486 A US523486 A US 523486A US 52348665 A US52348665 A US 52348665A US 3341376 A US3341376 A US 3341376A
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semiconductor material
semiconductor
crystal
tape
silicon
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Spenke Eberhard
Welker Heinrich
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Siemens Schuckertwerke AG
Siemens AG
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • 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
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/64—Flat crystals, e.g. plates, strips or discs
    • 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
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02373—Group 14 semiconducting materials
    • H01L21/02381—Silicon, silicon germanium, germanium
    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02387—Group 13/15 materials
    • H01L21/02395—Arsenides
    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/02543—Phosphides
    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/02546—Arsenides
    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • 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
    • Y10S117/903—Dendrite or web or cage technique
    • 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
    • Y10S148/00—Metal treatment
    • Y10S148/006—Apparatus
    • 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
    • Y10S148/00—Metal treatment
    • Y10S148/051—Etching
    • 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
    • Y10S148/00—Metal treatment
    • Y10S148/065—Gp III-V generic compounds-processing
    • 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
    • Y10S148/00—Metal treatment
    • Y10S148/067—Graded energy gap
    • 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
    • Y10S148/00—Metal treatment
    • Y10S148/072—Heterojunctions
    • 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
    • Y10S438/907—Continuous processing

Definitions

  • individual monocrystals of semiconductor substance in the form of discs are used as carriers, and a thin coating of the same semiconductor material, likewise monocrystalline, is precipitated thereupon.
  • the carrier discs can be severed, for example from semiconductor rods produced by a similar method. The production of such rods is described in the above-mentioned application Ser. No. 665,086.
  • the ultimate product is a rod-shaped monocrystal of extremely high degree of purity which can be sliced into discs suitable as fundamental body for semiconductor devices having several consecutive layers such as one or more p-n junctions, particularly for power rectifiers of high inverse blocking voltage, p-n junction transistors, controllable four-layer devices with thyratron or other gate charac teristics such as silicon controlled rectifiers. Due to the relatively large number of different processing steps required, the production of such semiconductor devices is rather intricate, expensive and results in a great deal of waste.
  • carrier for the pyrolytic precipitation of semiconductor substances not individual discs or rods, but rather long and flat tapes or strips. More particularly, we employ as the carrier crystal in the pyrolytic precipitation method, a semiconductor crystal produced by dendritic growth from a melt of the semiconductor material by pulling the crystal out of the melt in form of a long tape.
  • the drawing illustrates an apparatus for continuous production according to the invention.
  • Germanium, melting point 958 C. is melted, for example, in a graphite crucible, which is preferably heated inductively.
  • a corresponding placed upon the surface of the lower portion of the seed then will also melt.
  • a sudden supercooling of the melt at the seating location of the seed is effected, for example, by blowing a gaseous coolant, e.g. argon, onto the surface.
  • the supercooling is to about 10 C.
  • the seed is pulled upwardly out of the melt at relatively high speed, e.g. at a pulling speed more than 50 mm./min. In this manner a tape-shaped dendrite is produced.
  • the direction of growth is (211).
  • the lateral face of tape-shaped twin exhibit (111) orientation.
  • the width of the dendrite thus pulled may amount to 3 to 8 mm., the thickness of the tape to 500 microns, for example.
  • the length mainly depends upon the size of the pulling equipment.
  • the melting temperature of silicon is 1420 C.
  • the supercooling in this case may also amount to about 10 C.
  • the pulling speed must be greater than 40 mm./min. Since silicon cools better than germanium, the pulling speed can be less than with germanium.
  • the width of the pulled dendrites may be 3 to 8 mm., and their thickness 80 to 500 microns.
  • the melt, from which these tapes are pulled, may consist of doped or undoped semiconductor material. Further semiconductor material can be precipitated either upon one flat side only, or upon both flat sides of the tape. Since with ordinary dendritically grown monocrystals, one of the two flat sides has a more perfect structure than the dendritic crystal seed is germanium melt.
  • the dendritically grown tape to be used as the carrier crystal may consist of the same semiconductor material as that to be precipitated thereupon.
  • the carrier crystal may also consist of a different semiconductor material, provided it possesses the same lattice structure.
  • Particularly useful, for the purposes of the invention are the known semiconductor materials having a diamond lattice structure, such as germanium, silicon, and the A B intermetallic semiconductor compounds of elements from the third and fifth groups of the periodic system or intermetallic semiconductor compounds of elements of the second and sixth groups of the periodic system (ZnS).
  • ZnS intermetallic semiconductor compounds of elements from the third and fifth groups of the periodic system or intermetallic semiconductor compounds of elements of the second and sixth groups of the periodic system
  • a dendritically grown tape-shaped germanium carrier may be provided with a coating of gallium arsenide (GaAs) or another of the above-mentioned semiconducting intermetallic compounds.
  • GaAs gallium arsenide
  • a germanium layer may be precipitated upon a dendritic tape of monocrystalline silicon. A condition to be observed in each case is that the reaction temperature required for the pyrolytic production and precipitation of the coating material is less than the melting temperature of the carrier material.
  • the lattice constant of the semiconductor material to be precipitated thereon can differ from each other only up to about 5%. Consequently, for example, germanium can be precipitated upon silicon, gallium arsenide (GaAs) upon germanium, aluminum arsenide (AlAs) upon germanium as well as upon silicon, gallium arsenide (GaAs) upon aluminum arsenide and vice versa, aluminum phosphide ('AlP) upon silicon, gallium-phosphide (GaP) upon silicon, indiumphosphide (InP) upon germanium.
  • germanium can be precipitated upon silicon, gallium arsenide (GaAs) upon germanium, aluminum arsenide (AlAs) upon germanium as well as upon silicon, gallium arsenide (GaAs) upon aluminum arsenide and vice versa, aluminum phosphide ('AlP) upon silicon, gallium-phosphide (GaP) upon silicon, indiumphosphide (In
  • the transition from one element or compound to another may also include mixed crystals.
  • the process may be commenced by precipitating silicon, from a corresponding gaseous silicon compound such as silicon tetrachloride (SiCl or silico-chloroforrn (SiHCl).
  • SiCl silicon tetrachloride
  • SiHCl silico-chloroforrn
  • the semiconductor material pyrolytically produced by precipitation fromthe gaseous phase may be given an addition of doping substance during the reaction.
  • the doping concentration can be varied during the processing.
  • different layers of respectively different conductance type can be precipitated in order to thereby produce p-n junctions.
  • the method, of our invention permits the production of layers of extremely slight thickness with extreme uniformity. It permits observing minimum tolerances for any prescribed or desired layer thickness, accurate dosing of the doping concentration, and varying of that concentration to any degree over the layer thickness.
  • the method further affords producing any desired number of sequential layers differing from each other with respect to their height or/ and the type of conductance.
  • the novel method permits, among other things, the production of semiconductor structures or stratifications which can neither be obtained by the diffusion principle, nor by the alloying principle, nor by a combination of these two known types of methods.
  • the deposition of one or more coatings on a tape-shaped carrier crystal is made particularly economical by employing a continuous process.
  • the tape-shaped carrier crystal is sequentially passed through one or more spacially sequential furnaces or furnace portions which contain respective reaction chambers with gas inlet and outlet conduits and the required heating devices, and which are separated from each other and from the ambient atmosphere by gas locks.
  • the apparatus as illustrated in the drawing comprises a series of five interconnected chambers 1 to 5.
  • the dendrite 6 entering at 15 and exiting at 16 sequentially passes through chambers 1 to 5, for example at a rate of 45 mm./min.
  • the chamber 1 serves as a gas lock and is traversed by a current of protective gas for example argon or helium.
  • the protective gas enters at 8 and exits at 9.
  • the dendrite may have p-type conductance.
  • a reaction gas which imparts n-type conductance to the semiconductor material being precipitated is introduced at 10; the reacted gas exits at 11.
  • the gas may be hydrogen mixed with a corresponding silicon or germanium compound and an addition of a gaseous donor compound, for example a halide, particularly chloride, bromide or hydride of phosphorus or arsenic.
  • a gaseous donor compound for example a halide, particularly chloride, bromide or hydride of phosphorus or arsenic.
  • the chamber 3 serves as a gas lock and, like chamber 1, is traversed by a fiow of protective gas from 8 to 9.
  • Chamber 4 again serves precipitation purposes, in this case of p-type material.
  • the reaction gas mixture for chamber 4, which en: ters the chamber at 10, comprises an admixture of corresponding gaseous compounds of elements from the third group of the peroidic system.
  • the reacted gas exits at 11.
  • the chamber 5 again serves as a gas lock and is operated like chambers 1 and 3.
  • the introduction of the reaction gas into chambers 2 and 4 is preferably effected by nozzle means 14 in order to produce
  • the heating of the entire equipment can be effected by radiation or induction.
  • an induction winding 7 may be wound on the outside of the entire equipment in the direction of the travelling semiconductor tape.
  • the induction heating winding 7 may form a single circuit traversed by alternating current. However, the winding may also be separated at individual places and be supplied with different heating currents.
  • Heating of the dendrite tape by passing current directly therethrough is not feasible because, due to the progressing precipitation the tape possesses different cross section and different conductivity at different localities and hence does not have a uniform electric resistance over its entire length. If current were passed directly through the dendrite tape to heat the tape, it would be subjected to different degrees of heating at different localities with the result of obtaining differing rates of precipitation.
  • the inductive heating can be readily adapted to the different cross sectional and conductance conditions of the tape at different localities. This can be done in the above-described manner by subdividing the heater coil and applying different current intensities to the respective coil portions. However, the same effect can also be obtained by serially passing a current through all winding turns but giving the winding a greater number of turns per unit of length at some locations as compared with others.
  • a tape thus provided with one or more coatings can be cut into pieces having an area of any particular size desired, and these pieces need then only be provided with terminal contacts and a protective enclosure.
  • the protective enclosure may consist of a metallic housing or an insulating embedment produced, for example, by embedding the semiconductor device in synthetic resin.
  • the dendritically grown tape-shaped carrier crystals since they are produced by pulling them out of a crucible containing the semiconductor melt, are-not, as a rule, of such an extremely high degree of purity as carrier crystals produced without the use of a crucible. This, however, is not objectionable for many semiconductor devices because they must anyhow contain at least one highly doped layer. In many cases it is possible to have such a highly doped layer, which often constitutes an outer layer to be provided with a terminal contact, formed by the original carrier crystal. Layers of extremely high purity can be precipitated by chemical or pyrolytic reaction from gaseous mixtures that are purified to a correspondingly great extent, and can thus be precipitated as coatings upon a carrier crystal of lesser purity. Such extremely pure precipitated coatings are often applicable as base layers in transistors or other gating devices.
  • the preferred pyrolytic precipitation temperature for producing germanium from the corresponding germanium compounds is about 700 to 850 C. That is, the carrier crystal must be heated to this temperature. It is advisable to maintain the walls of the reaction vessel at a much lower temperature so that no precipitation will occur at these walls.
  • the production of a n-p-n transistor is carried out in the following manner.
  • the production is preferably started from a p-type twin having specific resistance from 80 to 240 ohm/cm.
  • a p-type twin having specific resistance from 80 to 240 ohm/cm.
  • Suitable for example, is a silicon crystal exhibiting a specific resistance of 200 to 240 ohm/ cm. and a thickness of 100 microns.
  • Precipitated upon both sides of the tWin crystal is a layer of n-type silicon with a thickness of 20 microns and a specific resistance of 0.01 ohm/cm. This can be done, for example, as follows:
  • Two silicon tapes are mounted in a reaction chamber, for example within a quartz vessel, and are heated to a temperature between about 1100 and about 1250 C.
  • the heating is preferably effected by electric inductance heating. However the tapes may also be heated by heat radiation.
  • a gaseous mixture is passed through the reaction chamber.
  • the mixture consists of hydrogen, which serves both as a carrier and as a reaction gas, and one or more of the abve-mentioned silicon compounds (SiCl SiHCl
  • the quantity of the gas mixture passing through the reaction chamber is approximately 0.5 to 30 liter per minute.
  • the molar ratio of the silicon compound to hydrogen, when using silicochloroform, is approximately 0.1, and when using silicon tetrachloride is about 0.05.
  • the corresponding silicochloroform-hydrogen mixture containing 2.10 grams of phosphorus trichloride (PCl per gram of silicochloroform, is passed through the reaction chamber for approximately 5 minutes in a quantity of 8 liters per minute.
  • the carrier gas (hydrogen) as well as the silicon compound are extremely purified prior to commencing the method.
  • Another example is the production of a four-layer semiconductor device of the p-n-p-n type. It is preferable to start with an n-type silicon twin dendrite having a specific resistance of 20 ohm/cm. and a thickness of 75 to 80 microns. At first, a p-type layer is precipitated upon both flat sides of the dendrite tape, with a layer thickness of 15 microns and a specific resistance of 2 ohm/cm. Thereafter a n-type layer, with a thickness of 15 microns and a specific resistance of 0.05 ohm/cm., is precipitated upon each of the p-type layers.
  • the pyrolytic precipitation can be effected from the corresponding silicon compounds.
  • the gas mixture may be given an addition of boron chloride (BCl
  • BCl boron chloride
  • PCl phosphorus trichloride
  • the electric connecting terminals, of the semiconductor circuit components produced in the above-described manner, can be eifected, for example by precipitating nickel from a bath of a corresponding nickel salt.
  • the attachment of the terminals may also be eifected by vapordeposition of metals, for example by placing metal foils, such as a gold foil, onto the circuit components device and alloying the materials together.
  • the overdoping may be effected by placing a boron-containing gold foil (with about 0.5% boron, the remainder being gold) upon the outer layer, the foil having a thickness of about 30 microns. Thereafter the foil is alloyed into the surface layer at a temperature of about 700 C.
  • the n-type layer is overdoped and now possesses p-type conductance and undisturbed surface proper, employing as the carrier crystal a semiconductor body yielded by dendritic growth from a melt of the last-mentioned semiconductor material by pulling a tape-shaped crystal out of a supercooled region of the melt, and removing some semiconductor material from the dendrite prior to the precipitation step so as to secure an undisturbed surface upon which monocrystalline growth can ensue.

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US523486A 1960-04-02 1965-12-13 Method of producing crystalline semiconductor material on a dendritic substrate Expired - Lifetime US3341376A (en)

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DES67895A DE1197058B (de) 1960-04-02 1960-04-02 Verfahren zur Herstellung einkristalliner flacher Halbleiterkoerper

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BE (1) BE601988A (fr)
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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3441453A (en) * 1966-12-21 1969-04-29 Texas Instruments Inc Method for making graded composition mixed compound semiconductor materials
US3473978A (en) * 1967-04-24 1969-10-21 Motorola Inc Epitaxial growth of germanium
US3473974A (en) * 1967-02-14 1969-10-21 Westinghouse Electric Corp Utilization of trace impurities in the vapor growth of crystals
US3493811A (en) * 1966-06-22 1970-02-03 Hewlett Packard Co Epitaxial semiconductor material on dissimilar substrate and method for producing the same
US3508962A (en) * 1966-02-03 1970-04-28 North American Rockwell Epitaxial growth process
US3635683A (en) * 1968-06-05 1972-01-18 Texas Instruments Inc Method of crystal growth by vapor deposition
US3893876A (en) * 1971-09-06 1975-07-08 Sumitomo Electric Industries Method and apparatus of the continuous preparation of epitaxial layers of semiconducting III-V compounds from vapor phase
US3907607A (en) * 1969-07-14 1975-09-23 Corning Glass Works Continuous processing of ribbon material
US3925118A (en) * 1971-04-15 1975-12-09 Philips Corp Method of depositing layers which mutually differ in composition onto a substrate
US3935040A (en) * 1971-10-20 1976-01-27 Harris Corporation Process for forming monolithic semiconductor display
US3984857A (en) * 1973-06-13 1976-10-05 Harris Corporation Heteroepitaxial displays
US3985590A (en) * 1973-06-13 1976-10-12 Harris Corporation Process for forming heteroepitaxial structure
US4089735A (en) * 1968-06-05 1978-05-16 Siemens Aktiengesellschaft Method for epitactic precipitation of crystalline material from a gaseous phase, particularly for semiconductors
US4309241A (en) * 1980-07-28 1982-01-05 Monsanto Company Gas curtain continuous chemical vapor deposition production of semiconductor bodies
US4419178A (en) * 1981-06-19 1983-12-06 Rode Daniel L Continuous ribbon epitaxy
US4464222A (en) * 1980-07-28 1984-08-07 Monsanto Company Process for increasing silicon thermal decomposition deposition rates from silicon halide-hydrogen reaction gases
US4727047A (en) * 1980-04-10 1988-02-23 Massachusetts Institute Of Technology Method of producing sheets of crystalline material
US4863760A (en) * 1987-12-04 1989-09-05 Hewlett-Packard Company High speed chemical vapor deposition process utilizing a reactor having a fiber coating liquid seal and a gas sea;
US5217564A (en) * 1980-04-10 1993-06-08 Massachusetts Institute Of Technology Method of producing sheets of crystalline material and devices made therefrom
US5273616A (en) * 1980-04-10 1993-12-28 Massachusetts Institute Of Technology Method of producing sheets of crystalline material and devices made therefrom
US5328549A (en) * 1980-04-10 1994-07-12 Massachusetts Institute Of Technology Method of producing sheets of crystalline material and devices made therefrom
US5362682A (en) * 1980-04-10 1994-11-08 Massachusetts Institute Of Technology Method of producing sheets of crystalline material and devices made therefrom
US5588994A (en) * 1980-04-10 1996-12-31 Massachusetts Institute Of Technology Method of producing sheets of crystalline material and devices made therefrom

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US2759848A (en) * 1954-12-28 1956-08-21 Bell Telephone Labor Inc Deposition of metal films from carbonyls
US2970068A (en) * 1955-03-07 1961-01-31 Union Carbide Corp Method of making a composite stock
US3030189A (en) * 1958-05-19 1962-04-17 Siemens Ag Methods of producing substances of highest purity, particularly electric semiconductors
US2995470A (en) * 1958-07-16 1961-08-08 Robbart Edward Method and apparatus for treating continuous lengths of material with gaseous compositions
US3031403A (en) * 1958-08-28 1962-04-24 Westinghouse Electric Corp Process for producing crystals and the products thereof
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Cited By (27)

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Publication number Priority date Publication date Assignee Title
US3508962A (en) * 1966-02-03 1970-04-28 North American Rockwell Epitaxial growth process
US3493811A (en) * 1966-06-22 1970-02-03 Hewlett Packard Co Epitaxial semiconductor material on dissimilar substrate and method for producing the same
US3441453A (en) * 1966-12-21 1969-04-29 Texas Instruments Inc Method for making graded composition mixed compound semiconductor materials
US3473974A (en) * 1967-02-14 1969-10-21 Westinghouse Electric Corp Utilization of trace impurities in the vapor growth of crystals
US3473978A (en) * 1967-04-24 1969-10-21 Motorola Inc Epitaxial growth of germanium
US4089735A (en) * 1968-06-05 1978-05-16 Siemens Aktiengesellschaft Method for epitactic precipitation of crystalline material from a gaseous phase, particularly for semiconductors
US3635683A (en) * 1968-06-05 1972-01-18 Texas Instruments Inc Method of crystal growth by vapor deposition
US3907607A (en) * 1969-07-14 1975-09-23 Corning Glass Works Continuous processing of ribbon material
US3925118A (en) * 1971-04-15 1975-12-09 Philips Corp Method of depositing layers which mutually differ in composition onto a substrate
US3893876A (en) * 1971-09-06 1975-07-08 Sumitomo Electric Industries Method and apparatus of the continuous preparation of epitaxial layers of semiconducting III-V compounds from vapor phase
US3935040A (en) * 1971-10-20 1976-01-27 Harris Corporation Process for forming monolithic semiconductor display
US3984857A (en) * 1973-06-13 1976-10-05 Harris Corporation Heteroepitaxial displays
US3985590A (en) * 1973-06-13 1976-10-12 Harris Corporation Process for forming heteroepitaxial structure
US5328549A (en) * 1980-04-10 1994-07-12 Massachusetts Institute Of Technology Method of producing sheets of crystalline material and devices made therefrom
US5217564A (en) * 1980-04-10 1993-06-08 Massachusetts Institute Of Technology Method of producing sheets of crystalline material and devices made therefrom
US5676752A (en) * 1980-04-10 1997-10-14 Massachusetts Institute Of Technology Method of producing sheets of crystalline material and devices made therefrom
US4727047A (en) * 1980-04-10 1988-02-23 Massachusetts Institute Of Technology Method of producing sheets of crystalline material
US4816420A (en) * 1980-04-10 1989-03-28 Massachusetts Institute Of Technology Method of producing tandem solar cell devices from sheets of crystalline material
US4837182A (en) * 1980-04-10 1989-06-06 Massachusetts Institute Of Technology Method of producing sheets of crystalline material
US5588994A (en) * 1980-04-10 1996-12-31 Massachusetts Institute Of Technology Method of producing sheets of crystalline material and devices made therefrom
US5549747A (en) * 1980-04-10 1996-08-27 Massachusetts Institute Of Technology Method of producing sheets of crystalline material and devices made therefrom
US5273616A (en) * 1980-04-10 1993-12-28 Massachusetts Institute Of Technology Method of producing sheets of crystalline material and devices made therefrom
US5362682A (en) * 1980-04-10 1994-11-08 Massachusetts Institute Of Technology Method of producing sheets of crystalline material and devices made therefrom
US4309241A (en) * 1980-07-28 1982-01-05 Monsanto Company Gas curtain continuous chemical vapor deposition production of semiconductor bodies
US4464222A (en) * 1980-07-28 1984-08-07 Monsanto Company Process for increasing silicon thermal decomposition deposition rates from silicon halide-hydrogen reaction gases
US4419178A (en) * 1981-06-19 1983-12-06 Rode Daniel L Continuous ribbon epitaxy
US4863760A (en) * 1987-12-04 1989-09-05 Hewlett-Packard Company High speed chemical vapor deposition process utilizing a reactor having a fiber coating liquid seal and a gas sea;

Also Published As

Publication number Publication date
GB949799A (en) 1964-02-19
NL262949A (fr) 1900-01-01
DE1197058B (de) 1965-07-22
BE601988A (fr) 1961-09-29
CH425738A (de) 1966-12-15

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