US3317354A - Process for doping a diamond in a gaseous electrical discharge - Google Patents

Process for doping a diamond in a gaseous electrical discharge Download PDF

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Publication number
US3317354A
US3317354A US370798A US37079864A US3317354A US 3317354 A US3317354 A US 3317354A US 370798 A US370798 A US 370798A US 37079864 A US37079864 A US 37079864A US 3317354 A US3317354 A US 3317354A
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Prior art keywords
diamond
chamber
cathode
glow discharge
anode
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US370798A
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English (en)
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Kenneth A Darrow
Jr Robert H Wentorf
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General Electric Co
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General Electric Co
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Priority to US370798A priority Critical patent/US3317354A/en
Priority to GB14926/65A priority patent/GB1101563A/en
Priority to FR16432A priority patent/FR1508064A/fr
Priority to DE1544190A priority patent/DE1544190C3/de
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/26Bombardment with radiation
    • H01L21/263Bombardment with radiation with high-energy radiation
    • H01L21/265Bombardment with radiation with high-energy radiation producing ion implantation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/25Diamond
    • C01B32/28After-treatment, e.g. purification, irradiation, separation or recovery
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C8/00Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/36Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-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
    • C30B31/00Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
    • C30B31/20Doping by irradiation with electromagnetic waves or by particle radiation
    • C30B31/22Doping by irradiation with electromagnetic waves or by particle radiation by ion-implantation

Definitions

  • the energy levels of the individual atoms forming the solid expand into energy bands. Between the several bands of energy levels are bands of forbidden energy levels in which electrons may not locate themselves.
  • the valence electrons of the individual atoms are located in the filled band of highest energy level, and above and below the band occupied by the valence electrons are regions having forhidden energy levels within which electrons cannot remain.
  • the resulting structure is an electronic semiconductor (an electronic conductor whose resistivity at room temperature is in the range of to 10- ohm-cm.) because impurities will have been introduced into the believingwhile insulator crystal, or else imperfections will have been impressed upon the crystal lattice of the pure substance.
  • an electronic semiconductor an electronic conductor whose resistivity at room temperature is in the range of to 10- ohm-cm.
  • impurities will have been introduced into the expectingwhile insulator crystal, or else imperfections will have been impressed upon the crystal lattice of the pure substance.
  • two types of semiconductors may be produced; the n-type (donor) extrinsic semiconductor and the p-type (acceptor) extrinsic semiconductor. These two types of semiconductors are distinguished from each other in that the sign of the Hall effect for the n-type is opposite to that for the p-type. More detailed information on the general theory of semiconduction and the manner for the preparation of semiconductors is set forth in the textbook, Applied Electronics, by
  • These an dother objects may be secured by subjecting diamond crystals to glow discharge ion bombardment under a voltage potential of at least 1.5 kilovolts for a period of time sufficient to modify the crystallinity of the outer surface of the diamond, so as to change the crys- 3,317,354 Patented May 2, 1967 talline nature thereof with respect to the diamond substrate.
  • FIG. 1 schematically represents a gas discharge apparatus suitable for the conduct of glow discharge ion bombardment in the practice of this invention
  • FIG. 2 is a graphic representation of the effect of temperature on the resistance of diamonds rendered semiconductive by the process of this invention.
  • one or more diamonds are placed within the gas discharge apparatus 10, shown in FIG. 1, within container 11 placed upon the metal receiver cathode 12, which is connected into the circuitry shown. It is preferable to clean the diamonds before placing them in apparatus 10, although small amounts of surface contamination may later be removed'while the diamonds are inside apparatus 10 by evacuation heating, an ion bombardment.
  • Bell jar 13, after being placed in sealing engagement with the surface of support 14, is evacuated by pipe 15 by means of a vacuum pump 16 to a pressure of about at least 10 mm. Hg.
  • Receiver cathode 12 is usually of nickel or molybdenum metal, and anode 17, made of the same metal as cathode 12, is located about l-inch thereabove.
  • a gas able to sustain a glow discharge is introduced into the bell jar through pipe 18 to a concentration providing a pressure ranging from about 10 to about 200 mm. Hg.
  • a voltage diiferential in excess of about 1500 volts is impressed between anode 17 and cathode 12 by means of D.C-. power supply'19.
  • gas-discharge currents of at least 20 milliamperes are produced whereby receiver cathode 12 is bombarded by ions of the gaseous environment, which bombarding ions have very high kinetic energies, i.e., in the order of about several hundred volts.
  • Example 1 Employing the apparatus disclosed and described herein in the conduct of this invention, nitrogen was employed as the gas within the bell jar at a pressure of 50 microns Hg at 30 C. Natural octahedral diamond crystals about 1 millimeter in size having electrical resistance of about ohms or greater at 25 C. (before treatment) were placed upon the receiver cathode and exposed to a glow discharge ion bombardment for a period of about 2 hours. The electrical resistance was measured in every instance by placing each crystal between massive silver electrodes and readings were taken with a sensitive electrometer. The crystals when removed from the glow discharge apparatus had a thin metallic film thereover, which film was removed when the crystals were cleaned with aqua regia and then with distilled water.
  • thermoelectric powers of the diamond crystals established that these crystals were n-type semiconductors having thermoelectric powers of the order of 10 microvolts per degree centigrade. Electron diffraction studies of the surfaces of these crystals indicated that these surfaces were decrystallized to a considerable extent, compared to the crystallinity of the original diamond material, to depths below the surface in the order of about 100 angstroms.
  • Example 2 Crystals of man-produced diamond were also subjected to substantially the same conditions as recited in Example 1. Comparable results were obtained.
  • Example 3 Crystals of cubic boron nitride produced in accordance with the teachings of US. 2,947,617 were subjected to substantially the same conditions as recited in Example 1 and contrary to the experience with diamond, the resistance of the cubic boron nitride crystals was increased slightly.
  • Example 4 The procedure set forth in Example 1 was repeated starting with p-type semiconducting diamons as, for example, may be prepared by another process. It was found that p-type semiconducting diamonds heavily doped with boron remained p-type semiconductors after exposure to glow discharge ion bombardment, but some aluminum-doped crystals were converted by ion bombardment with nitrogen from p-type to n-type semiconductors in their surface regions. This latter behavior suggests the possibility of making semiconducting devices, such as diodes or transistors, by preparing semiconducting diamond crystals by the high pressure methods disclosed in S.N. 130,439 (filed Aug. 9, 1961--Wentorf, Jr., et a1.) or S.N. 135,273 (filed Aug. 17, 1961-Cannon) and later to the ion-bombardment method disclosed herein.
  • Example 5 The general process described in Example 1 was repeated with argon substituted for nitrogen (analysis established that the argon contained in the order of 0.1 percent of nitrogen and 0.1 percent oxygen). After bombardment and cleaning with aqua regia and then distilled water, the diamond crystals were found to be n-type semiconductors with resistances of the magnitude recited in Example 1.
  • Example 6 Repetition of the process described in Example 1 cmploying hydrogen as the gaseous environment was found to produce p-type semiconductors with other electrical characteristics substantially as described in Example 1.
  • Example 7 Repetition of the process described in Example 1 employing helium as the gaseous environment was found to produce semiconducting crystals having room temperature resistances of about 10 -10 ohm but whose thermoelectric powers were too small to be detected.
  • FIG. 2 A graphic summary of the resistance behavior as a function of temperature for various semiconducting diamonds prepared by the method of this invention is shown in FIG. 2.
  • Each line with designations thereon indicates the formation of a p-type semiconductor with the particular gas; each line with (x) designations there along indicates an n-type semiconductor, and each line with 0) designations there along indicates formation of a semiconductor in terms of resistance qualities, but one having themoelectric powers too small to measure, indicating that both positive and negative carriers contribute about equally to the conductivity of these crystals.
  • Diamonds containing as much as 10 atoms per cubic centimeter of each of hydrogen and nitrogen have been produced by graphite-to-diamond conversion in the presence of known catalyst metals. These diamonds have been tested for their electrical properties and were found to be effec tive electrical insulators.
  • gas ions are actually driven into the surface of the diamond and are responsible for the contribution of a particular character to the semiconductor as being a p-type or an n-type semiconductor.
  • the reason for the difference in electrical behavior between a diamond crystal containing atoms as, for example hydrogen atoms, wherein the atoms were introduced during the creation of the crystal, and a diamond crystal wherein gas ions have been deliberately introduced by the practice of this invention is not known, but this difference in electrical behavior is manifest. Possibly of equal or of greater import as an explanation of this extraordinary behavior is the clear evidence of substantial physical disturbance to the diamond crystal in the surface regions thereof. This physical disturbance indicates the possibility of the rearrangement of the carbon atoms under the impact of the gas ions thereby rendering the surface less crystalline than it was in its original state.
  • n-type semiconducting diamond crystal prepared by the method of Example 1 was embedded in spectroscopic graphite in the reaction chamber of a high pressure apparatus such as is described in Hall-U.S. 2,941,248 and exposed for a period of about 12 minutes to the simultaneous application of about 63 kilobars of pressure and a temperature of about 1700 C. After this high pressure, high temperature exposure, the crystal was removed, cleaned in a hot mixture of sulfuric and nitric acids, then in distilled water, and then tested and was found to have lost its semiconducting properties.
  • n-type semiconducting diamond crystals prepared by the method of Example 1 are altered by exposure to temperature in the range of 300-400 C. for periods of an hour or more in air.
  • the gray-brown surface coloration of the crystals becomes less intense and their electrical resistances increase by factors of 10 to 1000. It is likely that this high temerature treatment improves the crystallinity of the surfaces and permits some of the trapped impurity atoms to leave the crystal.
  • a method for introducing additional allowed energy levels for electron occupancy into a material to selectively product semiconductor behavior by said material comprising the steps of:
  • said diamond material being disposed between said cathode and an anode spaced therefrom within said chamber
  • said gas being selected from the group consisting of nitrogen, hydrogen, oxygen, the noble gases and mixtures thereof, and being at a total internal gas pressure ranging between about 10 and about 200 microns of mercury,
  • a method for converting at least a portion of the surface of a p-type semiconductor diamond to function as an n-type semiconductor diamond comprising the steps of:
  • said diamond being disposed between said cathode and an anode spaced therefrom within said chamber
US370798A 1964-05-28 1964-05-28 Process for doping a diamond in a gaseous electrical discharge Expired - Lifetime US3317354A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US370798A US3317354A (en) 1964-05-28 1964-05-28 Process for doping a diamond in a gaseous electrical discharge
GB14926/65A GB1101563A (en) 1964-05-28 1965-04-08 Process for producing semi-conductor behavior in diamonds
FR16432A FR1508064A (fr) 1964-05-28 1965-05-10 Perfectionnements aux procédés pour conférer des propriétés semi-conductrices à certaines substances
DE1544190A DE1544190C3 (de) 1964-05-28 1965-05-26 Verfahren zum Einführen von Störstellen in Diamant

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DE (1) DE1544190C3 (de)
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GB (1) GB1101563A (de)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3383567A (en) * 1965-09-15 1968-05-14 Ion Physics Corp Solid state translating device comprising irradiation implanted conductivity ions
US3483443A (en) * 1967-09-28 1969-12-09 Hughes Aircraft Co Diode having large capacitance change related to minimal applied voltage
US4343628A (en) * 1981-01-27 1982-08-10 The United States Of America As Represented By The United States Department Of Energy Fluorinated diamond bonded in fluorocarbon resin
US4767517A (en) * 1983-11-28 1988-08-30 Kabushiki Kaisha Meidensha Process of depositing diamond-like thin film by cathode sputtering
US4844785A (en) * 1984-03-27 1989-07-04 Matsushita Electric Industrial Co., Ltd. Method for deposition of hard carbon film
US5145712A (en) * 1991-02-08 1992-09-08 Center For Innovative Technology Chemical deposition of diamond
US5182093A (en) * 1990-01-08 1993-01-26 Celestech, Inc. Diamond deposition cell
US5201986A (en) * 1990-08-07 1993-04-13 Sumitomo Electric Industries, Ltd. Diamond synthesizing method
US5227038A (en) * 1991-10-04 1993-07-13 William Marsh Rice University Electric arc process for making fullerenes
US5674572A (en) * 1993-05-21 1997-10-07 Trustees Of Boston University Enhanced adherence of diamond coatings employing pretreatment process
US7473410B1 (en) 1990-08-30 2009-01-06 Mitsubishi Corporation Form of carbon

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IE45102B1 (en) * 1976-07-21 1982-06-16 Gen Electric Process for converting type ib nitrogen in a diamond crystal into type ia nitrogen
GB1588445A (en) * 1977-05-26 1981-04-23 Nat Res Dev Toughening diamond
FR2393605A1 (fr) * 1977-06-09 1979-01-05 Nat Res Dev Procede de croissance de cristaux de diamant
IL79107A (en) * 1985-06-17 1989-03-31 De Beers Ind Diamond Ion implantation in crystalline substrate
DE3625743A1 (de) * 1986-07-30 1988-02-11 Winter & Sohn Ernst Verfahren zum bearbeiten von diamantkoernern
JPH05102068A (ja) * 1991-10-11 1993-04-23 Kobe Steel Ltd ダイヤモンドを用いた電子デバイスの電極形成方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2787564A (en) * 1954-10-28 1957-04-02 Bell Telephone Labor Inc Forming semiconductive devices by ionic bombardment
US3207582A (en) * 1960-03-12 1965-09-21 Inoue Kiyoshi Method of synthesizing diamond particles by utilizing electric discharge
US3233137A (en) * 1961-08-28 1966-02-01 Litton Systems Inc Method and apparatus for cleansing by ionic bombardment
US3256696A (en) * 1962-01-29 1966-06-21 Monsanto Co Thermoelectric unit and process of using to interconvert heat and electrical energy

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2787564A (en) * 1954-10-28 1957-04-02 Bell Telephone Labor Inc Forming semiconductive devices by ionic bombardment
US3207582A (en) * 1960-03-12 1965-09-21 Inoue Kiyoshi Method of synthesizing diamond particles by utilizing electric discharge
US3233137A (en) * 1961-08-28 1966-02-01 Litton Systems Inc Method and apparatus for cleansing by ionic bombardment
US3256696A (en) * 1962-01-29 1966-06-21 Monsanto Co Thermoelectric unit and process of using to interconvert heat and electrical energy

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3383567A (en) * 1965-09-15 1968-05-14 Ion Physics Corp Solid state translating device comprising irradiation implanted conductivity ions
US3483443A (en) * 1967-09-28 1969-12-09 Hughes Aircraft Co Diode having large capacitance change related to minimal applied voltage
US4343628A (en) * 1981-01-27 1982-08-10 The United States Of America As Represented By The United States Department Of Energy Fluorinated diamond bonded in fluorocarbon resin
US4767517A (en) * 1983-11-28 1988-08-30 Kabushiki Kaisha Meidensha Process of depositing diamond-like thin film by cathode sputtering
US4844785A (en) * 1984-03-27 1989-07-04 Matsushita Electric Industrial Co., Ltd. Method for deposition of hard carbon film
US5182093A (en) * 1990-01-08 1993-01-26 Celestech, Inc. Diamond deposition cell
US5201986A (en) * 1990-08-07 1993-04-13 Sumitomo Electric Industries, Ltd. Diamond synthesizing method
US7473410B1 (en) 1990-08-30 2009-01-06 Mitsubishi Corporation Form of carbon
US7976813B1 (en) 1990-08-30 2011-07-12 Mitsubishi Corporation Form of carbon
US8101149B1 (en) 1990-08-30 2012-01-24 Mitsubishi Corporation Form of carbon
US5145712A (en) * 1991-02-08 1992-09-08 Center For Innovative Technology Chemical deposition of diamond
US5227038A (en) * 1991-10-04 1993-07-13 William Marsh Rice University Electric arc process for making fullerenes
US5674572A (en) * 1993-05-21 1997-10-07 Trustees Of Boston University Enhanced adherence of diamond coatings employing pretreatment process

Also Published As

Publication number Publication date
FR1508064A (fr) 1968-01-05
DE1544190B2 (de) 1974-01-17
GB1101563A (en) 1968-01-31
DE1544190A1 (de) 1972-02-24
DE1544190C3 (de) 1974-08-15

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