US3108072A - Semiconductor process - Google Patents

Semiconductor process Download PDF

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Publication number
US3108072A
US3108072A US99906A US9990661A US3108072A US 3108072 A US3108072 A US 3108072A US 99906 A US99906 A US 99906A US 9990661 A US9990661 A US 9990661A US 3108072 A US3108072 A US 3108072A
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Prior art keywords
silicon
predetermined
resistivity
zone
rod
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US99906A
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English (en)
Inventor
Gutsche Heinrich
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Merck and Co Inc
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Merck and Co Inc
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Priority to NL276635D priority Critical patent/NL276635A/xx
US case filed in Illinois Northern District Court litigation Critical https://portal.unifiedpatents.com/litigation/Illinois%20Northern%20District%20Court/case/1%3A19-cv-06649 Source: District Court Jurisdiction: Illinois Northern District Court "Unified Patents Litigation Data" by Unified Patents is licensed under a Creative Commons Attribution 4.0 International License.
US case filed in Illinois Northern District Court litigation https://portal.unifiedpatents.com/litigation/Illinois%20Northern%20District%20Court/case/1%3A20-cv-03914 Source: District Court Jurisdiction: Illinois Northern District Court "Unified Patents Litigation Data" by Unified Patents is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Merck and Co Inc filed Critical Merck and Co Inc
Priority to US99906A priority patent/US3108072A/en
Priority to FR892283A priority patent/FR1318316A/fr
Priority to GB11739/62A priority patent/GB986546A/en
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Publication of US3108072A publication Critical patent/US3108072A/en
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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
    • 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

Definitions

  • This invention relates to a method of manufacture of semiconductor materials and, more particularly, to a method of producing uniformly-doped single crystals of semiconductor materials having predetermined resistivities.
  • the type of conductivity of semiconductor materials may be controlled by introducing certain foreign materials, generally termed impurities, into a melt of the semiconductive material.
  • impurities into the semiconductor ma terials
  • doping The introduction of such impurities into the semiconductor ma terials is usually referred to as doping.
  • the type of conductivity established in the semiconductor is dependent upon the electron configuration of the atoms of the impurity material and of the host crystal.
  • a substance whose atoms are capable of giving up electrons to the atoms of a particular substance is termed a donor impurity, and since there is a surplus of electrons available to carry a current, the semiconductor so doped is deemed to be of N-type (negative) conductivity.
  • acceptor impurity a substance whose atoms are capable of borrowing or accepting electrons is termed an acceptor impurity, and since there is a shortage of electrons in the crystal lattice available for current conduction, the semiconductor so doped is deemed to be of P-type (positive) conductivity.
  • Still another object of the instant invention is to provide uniformly doped single crystals of semiconductor material of predetermined conductivity type and resistivity wherein the resistivity level is achieved by adjusting the concentration of impurities in a master rod in a predetermined controlled manner, then diluting the concentration by controlled deposition thereon and thereafter zone refining the master rod during a selected number of Zone passes to further reduce the impurity concentration to the desired level.
  • FTGURE 1 is a flow sheet of the process steps of the present invention.
  • FIGURE 2 is a schematic illustration of suitable apparatus for use in the invention.
  • the desired resistivity level of the semiconductor material is achieved by doping a master semiconductor core of relatively small diameter to a predetermined relatively high doping level, then diluting the concentration by controlled deposition thereon of pure semiconductor material and thereafter decreasing this controlled level step-wise by vacuum zone refining, the extent of the decrease being a function of the pass speed and the number of zone passes to which the doped material is subjected.
  • the present process may be summarized by the process steps wherein there is first provided an elongated semiconductor rod in a reactor chamber onto which there is deposited, preferably from the vapor phase, an overlayer of like semiconductor material together with a very closely controlled, predetermined amount of conductivity determining impurities to achieve a desired impurity content proportional to a selected resistivity range.
  • a subsequent deposition of pure semiconductor material which is effected from the vapor phase the first deposited and precisely doped layer is overgrown and the impurity concentration of the final rod of relatively large diamete is arrived at by dilution in a predetermined manner.
  • the diluting step becomes one of high precision.
  • the subsequent deposition of pure semiconductor material can be effected either in the same reactor by simply interrupting the addition of doping impurities or the substrate core may be transferred from the doping reactor to a growth reactor after 2.
  • doped inner layer and potective outer layer has been deposited on the substrate in the doping reactor.
  • the latter practice is always desirable where one wishes to produc semeiconductor material of extremely high purity in one area or zone and has to confine all doping operations to another Zone which is well separated from the first one. Thereafter these rods are float zone refined for a selected number of zone passes at a constant travel rate whereby a certain fraction of the impurities is removed thereby providing a plurality of rods of different resistivity.
  • N-conductivity type silicon single crystals having predetermined resistivities in the range 0.1- ohm-cm. are produced by the steps of codepositing polycrystalline silicon from a thermally decomposable source of the material, such as silicochl roform, together within. a predetermined amount of phosphorus, from a vapor source of phosphorus trichloride, in the presence of hydrogen onto thin silicon substrate cores, then diluting the core by further deposition of relatively pure semiconductor material from the vapor phase and subsequently zone refining the doped cores in a controlled manner.
  • a thermally decomposable source of the material such as silicochl roform
  • FIGURE 2 there is shown in highly schematic form a suitable apparatus for carrying out the codeposition process from the vapor phase.
  • the apparatus includes a reaction chamber 2 in which is contained the silicon cores 1.
  • the core is resistively heated through a current source connected to the core through base 3.
  • a source of volatile semiconductor material such as trichlorosilane
  • trichlorosilane is then introduced into the reaction chamber through inlet 4 by passing hydrogen over liquid trichlorosilane 5.
  • a liquid phosphorus trichloride doping agent dissolved in trichlorosilane is contained in vessel 6.
  • a carefully measured amount of the liquid is then intro Jerusalem into the hydrogen-trichlorosilane gas stream.
  • Nozzle 7 serves to keep the gaseous reactants in a turbulent condition while in the reactor.
  • the sil icochloroform and the quantity of phosphorus trichloride are decomposed at a rapid rate onto the heated silicon cores thereby forming an overlayer of polycrystalline silicon uniformly doped with a carefully controlled concentration of phosphorus impurities.
  • 75x10 ml. of phosphorus trichloride dissolved in 12.5 ml. trichlorosilane (5.2 10 atoms P) are added dropwise to a gaseous mixture of one part silicochloroform to nine parts hydrogen at flow rates of 500 g. SiHCl and 12 liters H respectively, in the presence of polycrystalline silicon cores each having a length of about 12 inches and a diameter of 5 mm.
  • the cores are heated at 1150 C. during about 15 hours. During the initial deposition all the phosphorus is deposited. Thereafter the diameter of the core is increased by a predetermined amount controlled by the overall time of deposition at given flow rates in accordance with the resistivity level desired for the material. For example, approximately 400 g. of silicon are deposited. The silicon contains a uniform distribution along the length of the rod of 3 1tl atoms of phosphorus per cc. which is equivalent to a resistivity of 0.2 ohm-cm. This adjustment in impurity content quite nearly determines the resistivity level of the resultant single crystal semiconductor material produced during subsequent steps in the process.
  • the doped rods are float zone refined in any conventional vacuum zone refining apparatus well known in the art and described in detail, for example, in U.S. Patent 2,901,325.
  • float zone refining involves mounting the semiconductor rod in a vacuum with a heating coil around it, and movin" the coil at a prescribed travel rate along the length of the rod.
  • a standard travel rate of 3 mm. per minute is used.
  • resistivity level of the doped rods is merely a function of the number of zone passes of the coil, namely the number of complete traversals of the length of the crystal by the moving coil.
  • the resistivity of the resultant single crystal rod was 0.24 ohm-cm; after two passes, 0.36; after three passes, 0.5; after four passes, 0.89; and after seven passes, 4.2.
  • a method of forming a single crystal silicon semiconductor material having uniform predetermined resistivity and N conductivity type within the range 2-66 ohm-cm. which comprises providing a uniform elongated silicon core of given diameter, codepositing silicon and phosphorus onto said core from the vapor phase by thermal decomposition of a vapor formed from 0.2 50 ml. of a solution containing silicochloroform and phosphorus trichloride in a ratio of 6X10 ml. PCl /ml.
  • a method of forming a single crystal silicon rod having a resistivity of 0.36 ohm-cm. N which comprises providing a silicon semiconductor rod having a diameter of 5 mm. and a length of 12 inches, heating said rod to 1150 C., introducing a gaseous mixture of one part silicochloroform to 9 parts of hydrogen at a flow rate of 500 g. SiHCl per hour and 12 liters H per minute respectively together with 7.5 10- m1. of phosphorus trichloride, continuing said heating for about 15 hours to produce an overlayer of about 400 g.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
US99906A 1961-03-31 1961-03-31 Semiconductor process Expired - Lifetime US3108072A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
NL276635D NL276635A (en, 2012) 1961-03-31
US99906A US3108072A (en) 1961-03-31 1961-03-31 Semiconductor process
FR892283A FR1318316A (fr) 1961-03-31 1962-03-26 Procédé de fabrication d'une matière monocristalline semi-conductrice
GB11739/62A GB986546A (en) 1961-03-31 1962-03-27 Semiconductor

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US99906A US3108072A (en) 1961-03-31 1961-03-31 Semiconductor process

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GB (1) GB986546A (en, 2012)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3192083A (en) * 1961-05-16 1965-06-29 Siemens Ag Method for controlling donor and acceptor impurities on gaseous vapor through the use of hydrogen halide gas
US3332796A (en) * 1961-06-26 1967-07-25 Philips Corp Preparing nickel ferrite single crystals on a monocrystalline substrate
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
WO2014093087A1 (en) * 2012-12-11 2014-06-19 Hemlock Semiconductor Corporation Methods of forming and analyzing doped silicon
US11051890B2 (en) 2014-02-27 2021-07-06 University Surgical Associates, Inc. Interactive display for surgery with mother and daughter video feeds

Citations (5)

* 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
US2910394A (en) * 1953-10-02 1959-10-27 Int Standard Electric Corp Production of semi-conductor material for rectifiers
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
US3011877A (en) * 1956-06-25 1961-12-05 Siemens Ag Production of high-purity semiconductor materials for electrical purposes

Patent Citations (5)

* 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
US2910394A (en) * 1953-10-02 1959-10-27 Int Standard Electric Corp Production of semi-conductor material for rectifiers
US2964396A (en) * 1954-05-24 1960-12-13 Siemens Ag Producing semiconductor substances of highest purity
US3011877A (en) * 1956-06-25 1961-12-05 Siemens Ag Production of high-purity semiconductor materials for electrical purposes
US2970111A (en) * 1958-09-20 1961-01-31 Siemens Ag Method of producing a rod of lowohmic semiconductor material

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3192083A (en) * 1961-05-16 1965-06-29 Siemens Ag Method for controlling donor and acceptor impurities on gaseous vapor through the use of hydrogen halide gas
US3332796A (en) * 1961-06-26 1967-07-25 Philips Corp Preparing nickel ferrite single crystals on a monocrystalline substrate
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
WO2014093087A1 (en) * 2012-12-11 2014-06-19 Hemlock Semiconductor Corporation Methods of forming and analyzing doped silicon
US11051890B2 (en) 2014-02-27 2021-07-06 University Surgical Associates, Inc. Interactive display for surgery with mother and daughter video feeds

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GB986546A (en) 1965-03-17
NL276635A (en, 2012)

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