US3394085A - Methods of producing zinc-doped gallium phosphide - Google Patents

Methods of producing zinc-doped gallium phosphide Download PDF

Info

Publication number
US3394085A
US3394085A US479556A US47955665A US3394085A US 3394085 A US3394085 A US 3394085A US 479556 A US479556 A US 479556A US 47955665 A US47955665 A US 47955665A US 3394085 A US3394085 A US 3394085A
Authority
US
United States
Prior art keywords
zinc
melt
gallium phosphide
gallium
doped gallium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US479556A
Other languages
English (en)
Inventor
Westerveld Willem
Graaf Wilhelmus Polycarpus De
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
US Philips Corp
North American Philips Co Inc
Original Assignee
US Philips Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by US Philips Corp filed Critical US Philips Corp
Application granted granted Critical
Publication of US3394085A publication Critical patent/US3394085A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
    • C30B31/04—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor by contacting with diffusion materials in the liquid state
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/4554—Coating
    • H01L2224/45565—Single coating layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/484—Connecting portions
    • H01L2224/48463—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
    • H01L2224/4901—Structure
    • H01L2224/4903—Connectors having different sizes, e.g. different diameters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00011—Not relevant to the scope of the group, the symbol of which is combined with the symbol of this group
    • 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
    • Y10S148/107—Melt

Definitions

  • the invention relates to an injection radiation source having a body of gallium phosphide containing zinc in solid solution and an electrode from where excess charge carriers can be injected into the zinc-doped gallium phosphide body, so that in the recombination process of electrons and holes in the body radiation can be produced, and relates furthermore to a method of producing zinc doped gallium phosphide by separation from a melt consisting mainly of gallium and phosphorus and furthermore zinc.
  • the recombination need not be a direct combination of an electron in the conduction band with a hole in the valence band, it may also be performed stepwise, for example by the capture of an electron from the conduction band or a hole from the valence band in an intermediate level, after which they are recombined with a hole and an electron respectively, while during at least one of the steps radiation is produced. Instead of two steps the recombination may be performed in three or more steps.
  • Such a radiation source may be employed for many purposes, for example as a lamp, in electronic, optical or electro-optical devices, having at least one electro-luminescent part for example signal transmission systems with electroluminescent cells and photocells, in image intensifiers with photo-electric and electro-luminescent layers, in opto-electronic transistors and in so-called lasers, having an injection radiation source in which stimulated coherent radiation is produced.
  • the radiation may be produced in the semi-conductor material for example by the passage of current through a p-n, p-i-n, or metal-semiconductor junction.
  • zinc-doped gallium phosphide is a particularly suitable material for use in an injection radiation source in which radiation is produced in the visible region of the spectrum with a maximum at about 7000 A. and 5750 A.
  • the yield may be very high.
  • the melt contains furthermore constituents reacting readily with oxygen.
  • Solid gallium oxide may be formed in the melt.
  • the particles thereof may operate as crystallising seeds, so that the formation of generally desired monocrystals of reasonable size is counteracted.
  • such particles may from inclusions in the gallium phosphide bodies obtained, which might absorb part of the radiation, when such a body is employed in a radiation source.
  • the invention has for its object inter alia to provide zinc-doped gallium phosphide suitable for use in an injection radiation source, which does not display said disadvantages. It has now been found that gallium phosphide obtained from an oxygen-free melt of gallium, phosphorus and zinc does not contain detectable quantities of zinc, while such a melt, which furthermore contains a small quantity of oxygen, can provide gallium phosphide containing zinc in quantities which can be readily detected spectrographically. Therefore, it is possible that the addition of oxygen has the function of enabling the incorporation of zinc in the crystal lattice of gallium phosphide. It has now been found that instead of oxygen also the presence of other elements permit of obtaining gallium phosphide with zinc doping, suitable for use in an injection radiation source.
  • an injection radiation source of the kind set forth is characterized in that the zinc-doped gallium phosphide of at least that part of the body into which the excess charge carriers can be injected from the electrode, contains, in addition, tin and/ or germanium.
  • the zinc-doped gallium phosphide of at least that part of the body into which the excess charge carriers can be injected from the electrode contains, in addition, tin and/ or germanium.
  • a zinc content of at least 0.0005 by weight is preferably made of a zinc content of at least 0.0005 by weight. With a zinc content in excess of 0.01% by weight the intensity of the radiation emanating from the gallium phosphide is considerably reduced by internal absorption so that a less high zinc concentration is preferred.
  • a method of producing zinc-doped gallium phosphide by separation from a melt containing mainly gallium and phosphorus and furthermore zinc is characterized in that the melt contains, in addition, tin and/ or germanium.
  • the melt contains, in addition, tin and/ or germanium.
  • Gallium phosphide doped with zinc may be used in injection radiation sources, but the method according to the second aspect of the invention is not restricted to the production of material for this use; if desired, the material produced by said method may also 'be used, in principle, for other semi-conductor devices for example diodes and transistors.
  • oxygenfree as used in the claims is intended to denote an atmosphere substantially equivalent to that obtained by exhaustion and back filling as described in the working example hereinafter.
  • the atomic quantity of gallium in the melt is preferably chosen higher than the sum of the atomic quantities of the other elements in the melt. This involves that it is not necessary to carry out the formation of the melt and the separation of gallium phosphide therefrom at extremely high temperatures, while gallium phosphide crystals with a substantially constant zinc concentration may be obtained therefrom without appreciable concentration gradients.
  • the atomic quantity of gallium in the melt is preferably at least twice the atomic quantity of phosphorus therein. In practice, it is preferred to prepare a melt having an atomic quantity of gallium at least five times and at the most twenty times the atomic quantity of phosphorus in the melt.
  • the zinc content in the melt preferably amounts to at least 0.001% by Weight and at the most 0.2% by weight and if no germanium is added to the material to be melted the tin content is preferably at least 0.001% and at the most 1% by weight.
  • the melt is preferably cooled gradually down from a temperature of at least 900 C.
  • the zinc-doped gallium phosphide crystals formed can be separated from the solidified gallium by dissolving the gallium in 36% by weight of hydrochloric acid.
  • the crystals obtained may be sorted to size and, if desired, larger crystals may be divided into smaller monocrystal bodies of the desired dimensions.
  • the body 1 of this example (see the figure) has a length of about 4 mms., a width of about 2 mms. and a thickness of about 0.3 mm.
  • Onto one side of the body 1 are alloyed two metal pellets.
  • One pellet has a diameter of 400 to 500,12 and consists of an alloy of gold and zinc (4% by weight of zinc).
  • the second pellet has a diameter of about 300, and consists of tin.
  • the two pellets are alloyed at a temperature of 1000 C. to 1100 C.
  • the gold-andzinc pellet constitutes an ohmic contact 2 with the body 1 and the tin pellet constitutes a rectifying contact 3 with the body 1.
  • the rectifying contact 3 constitutes the injecting electrode of the light source.
  • Tin-clad copper wires 4 and 5 are soldered to the contacts.
  • a voltage of 2.2 v. is applied in the forward direction between the contacts, so that in the body 1, in the proximity of the contact 3, there is produced an intensive orange-red radiation with a maximum of about 7000 A. and a maximum of about 5750 A.
  • a method of producing zinc-doped gallium phosphide crystals comprising forming a melt consisting essentially of gallium and phosphorus as the main constituents, a minor amount of zinc as a dopant, and in addition a minor amount of at least One element selected from the group consisting of tin and germanium, the gallium being present in the melt in an atomic quantity which exceeds the sum of the atomic quantities of all the other elements, cooling said melt to form said doped crystals, and separating said crystals from the excess gallium present, said melt-forming and cooling steps being effected in an oxygenfree atmosphere.
  • a method as set forth in claim 2 wherein the zinc content in the melt is between 0.001% and 0.2% by weight.
  • melt contains tin, and the tin content is between 0.001% and 1% by weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Led Devices (AREA)
  • Catalysts (AREA)
US479556A 1964-08-29 1965-08-13 Methods of producing zinc-doped gallium phosphide Expired - Lifetime US3394085A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL6410080A NL6410080A (enrdf_load_stackoverflow) 1964-08-29 1964-08-29

Publications (1)

Publication Number Publication Date
US3394085A true US3394085A (en) 1968-07-23

Family

ID=19790909

Family Applications (1)

Application Number Title Priority Date Filing Date
US479556A Expired - Lifetime US3394085A (en) 1964-08-29 1965-08-13 Methods of producing zinc-doped gallium phosphide

Country Status (8)

Country Link
US (1) US3394085A (enrdf_load_stackoverflow)
AT (1) AT270748B (enrdf_load_stackoverflow)
BE (1) BE668878A (enrdf_load_stackoverflow)
CH (1) CH477915A (enrdf_load_stackoverflow)
DE (1) DE1272452B (enrdf_load_stackoverflow)
GB (1) GB1043689A (enrdf_load_stackoverflow)
NL (1) NL6410080A (enrdf_load_stackoverflow)
SE (1) SE321298B (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549401A (en) * 1966-12-20 1970-12-22 Ibm Method of making electroluminescent gallium phosphide diodes
US3872490A (en) * 1970-11-16 1975-03-18 Omron Tateisi Electronics Co Mechanical - electrical semiconductor transducer with rectifying tin oxide junction
US5349208A (en) * 1992-11-07 1994-09-20 Shin Etsu Handotai Kabushiki Kaisha GaP light emitting element substrate with oxygen doped buffer

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3290539A (en) * 1963-09-16 1966-12-06 Rca Corp Planar p-nu junction light source with reflector means to collimate the emitted light
US3293513A (en) * 1962-08-08 1966-12-20 Texas Instruments Inc Semiconductor radiant diode

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT228858B (de) * 1961-02-07 1963-08-12 Philips Nv Elektro-optische Halbleitervorrichtung

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293513A (en) * 1962-08-08 1966-12-20 Texas Instruments Inc Semiconductor radiant diode
US3290539A (en) * 1963-09-16 1966-12-06 Rca Corp Planar p-nu junction light source with reflector means to collimate the emitted light

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549401A (en) * 1966-12-20 1970-12-22 Ibm Method of making electroluminescent gallium phosphide diodes
US3872490A (en) * 1970-11-16 1975-03-18 Omron Tateisi Electronics Co Mechanical - electrical semiconductor transducer with rectifying tin oxide junction
US5349208A (en) * 1992-11-07 1994-09-20 Shin Etsu Handotai Kabushiki Kaisha GaP light emitting element substrate with oxygen doped buffer

Also Published As

Publication number Publication date
AT270748B (de) 1969-05-12
NL6410080A (enrdf_load_stackoverflow) 1966-03-01
SE321298B (enrdf_load_stackoverflow) 1970-03-02
DE1272452B (de) 1968-07-11
GB1043689A (en) 1966-09-21
CH477915A (de) 1969-09-15
BE668878A (enrdf_load_stackoverflow) 1966-02-28

Similar Documents

Publication Publication Date Title
US3458779A (en) Sic p-n junction electroluminescent diode with a donor concentration diminishing from the junction to one surface and an acceptor concentration increasing in the same region
Migliorato et al. Analysis of the electrical and luminescent properties of CuInSe2
Gershenzon et al. Electroluminescence at p‐n Junctions in Gallium Phosphide
EP0368854B1 (en) Silicon electroluminescent device
Casey Jr et al. Single crystal electroluminescent materials
US2900286A (en) Method of manufacturing semiconductive bodies
US3603833A (en) Electroluminescent junction semiconductor with controllable combination colors
US3931631A (en) Gallium phosphide light-emitting diodes
US3690964A (en) Electroluminescent device
DE2131391C2 (de) Elektroluminierende Galliumphosphid-Diode
Starkiewicz et al. Injection electroluminescence at pn junctions in zinc-doped gallium phosphide
US3302051A (en) Semiconductive alloy light source having improved optical transmissivity
US4001056A (en) Epitaxial deposition of iii-v compounds containing isoelectronic impurities
US3549434A (en) Low resisitivity group iib-vib compounds and method of formation
US3394085A (en) Methods of producing zinc-doped gallium phosphide
US3496429A (en) Solid state light sources
US3390311A (en) Seleno-telluride p-nu junction device utilizing deep trapping states
Saul et al. Distribution of impurities in Zn, O‐doped GaP liquid phase epitaxy layers
US3365630A (en) Electroluminescent gallium phosphide crystal with three dopants
US4001055A (en) Semiconductor light-emitting diode and method for producing same
US3986193A (en) Semiconductor SiCl light source and a method of manufacturing same
US3245847A (en) Method of producing stable gallium arsenide and semiconductor diodes made therefrom
US3326730A (en) Preparing group ii-vi compound semiconductor devices
GB781795A (en) Improvements relating to the manufacture of p-n junction devices
US3414441A (en) Electroluminescent junction device including a bismuth doped group iii(a)-v(a) composition