US3302051A - Semiconductive alloy light source having improved optical transmissivity - Google Patents

Semiconductive alloy light source having improved optical transmissivity Download PDF

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US3302051A
US3302051A US330173A US33017363A US3302051A US 3302051 A US3302051 A US 3302051A US 330173 A US330173 A US 330173A US 33017363 A US33017363 A US 33017363A US 3302051 A US3302051 A US 3302051A
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Simeon V Galginaitis
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General Electric Co
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of group III and group V of the periodic system
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/20—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular shape, e.g. curved or truncated substrate
    • 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
    • Y10S148/107—Melt
    • 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
    • Y10S438/936—Graded energy gap

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  • Led Devices (AREA)

Description

ENERGY Jan. 31, 1967 s. v. GALGINAITIS 3,302,051
SEMICONDUCTIVE ALLOY LIGHT SOURCE HAVING IMPROVED QPTICAL THANSMISSIVITY Filed Dec. 12, 1963 Fl'gj Inventor-2r 8 r1 VGZ/ ind/'f/s b) Fe g 4 s Attorney.
DISTANCE United States Patent 6 l 3,302,051 SEMICONDUCTIVE ALLOY LIGHT SOURCE HAV- ING IMPROVED OPTICAL TRANSMISSIVITY Simeon V. Galginaitis, Schenectady, N.Y., assignor to General Electric Company, a corporation of New York Filed Dec. 12, 1963, Ser. No. 330,173 Claims. (Cl. 313-108) The present invention relates generally to semiconductive light sources and more particularly pertains to means for etficiently extracting the radiation generated within such a light source.
There are a plurality of semiconductive materials, as gallium arsenide, for example, that are known to provide efiicient electroluminescence in response to electrical excitation. A particularly eilicient group, of semiconductive light sources, is that wherein the source of radiation is a P-N junction formed in the semiconductive material. Such light sources are disclosed, for example, in Physical Review Letters, vol. 9, p. 366 (1962), by R. N. Hall, G. E. Fenner, J. D. Kingsley, T. J. Soltys and R. O. Carlson, wherein efficient light production at a P-N junction is disclosed to produce coherent radiation within the semiconductive mate-rial.
While semiconductive junction light sources exhibit eflicient gene-ration of light within the semiconductive material, the more desirable semiconductive materials for this purpose possess high dielectric constants, high optical refractive indices and great absorptivity. The difficulties associated with the former two characteristics are substantially overcome through practice of the invention by W. Engeler, disclosed and claimed in copending application, Serial No. 330,172, filed concurrently herewith. It would be highly desirable to reduce the a-bsorptivity of the semiconductive material and provide a further increase in luminous efiiciency.
Accordingly, it is an object of my invention to provide a more efiicient light source fabricated from semiconductive materials.
Another object of my invention is to provide a P-N junction light source having reduced absorptivity of the light generated within the junction.
Still another object of my invention is to reduce the absorption of radiation within a semi-conductive body.
Briefly, in accord with a preferred embodiment of my invention, I provide an alloy semiconductive body wherein the concentrations of constituents varies along at least one dimension of the body. The concentrations of constituents are selected to provide one region in the semiconductive body having a lower band-gap energy than the remainder of the body. A P-N junction is formed in the low band-gap energy region and the remainder of the body is adapted to transmit radiation originating at the PN junction. Thus, radiation originating in the vicinity of the junction is in quanta that are unable to interact with electrons in the higher band-gap mate-rial and absorptivity of the portion of the semiconductive body that is adapted to transmit the radiation is greatly reduced.
The features of my invention which I believe to be novel are set forth with particularity in the appended claims. My invention itself, however, both as to its organization and method of operation, together with further objects and advantages thereof, may best be understood by reference to the following description taken in connection with the accompanying drawing in which:
FIGURE 1 is a cross-sectional view of a light source embodying my invention;
FIGURE 2 is a cross sectional view of another light source embodying the present invention; and,
FIGURE 3 is a diagram illustrating the energy band- 3,302,051 Patented Jan. 31, l96'7 "ice gap variation in a device fabricated in accord with this invention.
Photons are emitted in a semiconductive body in response to an electron, that possesses an energy near or equal to that of the conduction band, dropping down in energy by an amount substantially equal to the bandgap of the material, to possess an energy near or equal to that of the valence band. The photon emitted is substantially equal in energy to the energy given up by the electron, and consequently is substantially equal to the band-gap energy of the material. The latter defines the difference in energy between the edges of the conduction and valence bands.
Absorption in a semiconductive material is most commonly associated with a photon giving up its energy to an electron which is consequently raised from an energy about equal to that of the valence band to an energy near or equal to that of the conduction band, resulting in an electron-hole pair. When the energy of the photon is so low that it is incapable of raising the energy of an electron by an amount approximately equal to the bandgap energy, this form of photon absorption does not occur and the semiconductive material appears substantially transparent to the photon, though, there are secondary effects present of lesser consequence associated with structural defects, impurities and free carriers.
In accord with my invention I provide a semiconductive crystal body that is constituted of an alloy semiconductive material wherein the concentrations of constituents varies, progressing along the body in at least one direction. An electroluminescent P-N junction is formed in the region of the semiconductive body possessing the lower band-gap energy. The remainder of the semiconductive body is then formed or shaped to provide an efficient structure for extracting the radiation, that is either coherent or incoherent, from the semiconductive body. This portion, by virtue of its greater band-gap energy, is substantially transparent to photons originating at the P-N junction.
In general, a semiconductive crystal suitable for use in accord with the present invention is, conveniently, fabricated from two mutually soluble semiconductive materials that are mixed, melted, and recrystallized by any of a plurality of known techniques including seed crystal withdrawal and zone refining. The semiconductive constituents are selected to exhibit ditferent band-gaps. Normally, the portion of the semiconductive alloy having the greater concentration of the lower band-gap material provides the optimum region for forming the PN junction. The variation in constituent concentrations advantageously progresses slowly, and preferably uniformly, throughout the body by varying a parameter, as temperature, during the recrystallization phase of the process. The reason that gradual changes are preferred is to ensure minimum discontinuities in the body that can provide reflections and other undesirable optical and/or solid state effects. The vapor transport crystal growing technique has proved particularly efiicient in producing crystals suitable for use in accord with my invention. The constituent having the greater dissociation pressure (generally the constituent with the lower melting temperature) is initially grown in a concentration that is less than its presence in the source by a percentage that increases as the temperature with which the transport is carried out increases.
Preferred practice of the present invention is with an alloy semiconductive body constituted essentially of two mutually soluble constituents selected from the Group III-V and II-VI compounds (of the Periodic Chart of the elements). Particularly desirable combinations of the Group III-V compounds includes (GaAs-GaP), (InAs- GaAs), (InAs-InP) and (GaSb-InSb); while correspondingly desirable combinations of the Group II-VI compounds include (ZnTe-CdTe), (ZnSe-ZnS), (ZnSe-ZnTe), (CdS-ZnS), and (CdS-CdSe). Alloys constituted of one or more elemental semiconductive materials, as silicon and germanium, are used to equal advantage in applications wherein the band-gap of the material is substantially greater than the energy of the photons being transmitted. Indeed, practice of the invention is not limited to an alloy constituted of semiconductors but equally includes combinations of metals, as antimony and bismuth, that are mutually soluble and combine to provide a semiconductive material. It is only necessary that a semiconductive body be provided having portions thereof of differing band-gap energies, andpreferably, having a gradual, uniform variation in energy difference between the valence and conduction band edges throughout the body progressing in a given direction.
Particularly suitable constituents for the semiconductive body used in the practice of this invention are gallium arsenide and gallium phosphide. The reasons for this selection include the highly desirable electroluminescence properties of PN junctions formed in alloys of these constituents and the complete mutual solubility that enables all alloy concentrations of these materials to be formed readily by techniques well-known in the art including the various controlled directional crystallization processes and vapor transport techniques. The latter technique has been discovered to offer particular advantages and has been conducted as set forth below.
A container fabricated of inert refractory material, as fused quartz, was filled with a mixture of gallium arsenide and gallium phosphide. The container was suspended over a gallium arsenide substrate in a sealed enclosure filled with hydrogen chloride gas. The temperature of the gallium arsenide and gallium phosphide was raised to a temperature of 850 C. by radiant heating and the gallium arsenide substrate was maintained at a lower temperature of 800 C. The gases that filled the sealed container included gallium chloride, arsenic, phosphorus and hydrogen. Under the aforementioned conditions the crystal growth rate on the substrate was discovered to be about of a millimeter per hour. The gallium arsenide substrate was then recovered from the sealed container after ten hours and a one millimeter thick wafer was cut from the exposed surface of the substrate. The surface of the wafer that had been first grown on the substrate contained 81 mole percent gallium arsenide and 19 percent gallium phosphide. The last portion of the crystal to grow contained 76 mole percent gallium arsennide and 24 mole percent gallium phosphide. The change in concentration occurred gradually and substantially uniformly from one surface to the other. Similarly, the band-gap varied substantially uniformly from a lowest band-gap at the surface containing the lesser concentration of gallium phosphide to a maximum band-gap at the opposite surface. Thus, in the preceding way a crystal was produced particularly suited for use in accord with my invention.
FIGURES 1 and 2 illustrate light sources in accord with the present invention that feature a portion of the semiconductive crystal formed to provide optical means for extracting radiation originating in a P-N junction. FIGURE 1 illustrates a reflector structure and FIGURE 2 shows a lens structure.
The light source shown in FIGURE 1 features a semiconductive material of variable band-gap having surface 1 ground in the general form of a paraboloid. The opposing fiat surface 2 surrounds a centrally disposed mesa 3 that is advantageously formed by masking and etching. A junction 4 is formed in the mesa by any of a plurality of well-known techniques, including diffusion of an acceptor impurity, as zinc in the case of (GaAs-GaP). Suitable electrical contacts 5 and 6 provide the required electrical excitation of junction 4 from electrical source 7 that is required to provide generation of photons at 4 junction 4. Radiation 8 from junction 4 is reflected by paraboloid curved surface 1 out through flat surface 2. Surface 1 can include a reflecting coating, and surface 2 can include an anti-reflecting coating.
In accord with my invention the band-gap of the semiconductive material in the vicinity of junction 4 is less than the band-gap of the material from which reflector 9 is constituted. Thus, absorption of radiation 8 is minimized in solid reflector 9.
In the event that the light source of FIGURE 1 is fabricated from a gallium arsenide-gallium phosphide crystal of the type previously described, the semiconductive material in the vicinity of mesa 3 is constituted of about 81 mole percent gallium arsenide, remainder essentially gallium phosphide, and the semiconductive material in the vicinity of the point of symmetry on curved surface 1 is constituted of about 76 mole percent gallium arsenide, remainder essentially gallium phosphide. Other concentrations are equally acceptable so long as the minimum gallium arsenide concentration in the vicinity of the junction is in excess of about 50 mole percent. The precise composition at the junction, for example, determines the wavelength of radiation. Highest energy per photon is achieved with approximately a 50/50 composition in the solid solution under consideration. With these materials, radiation 8 incident upon surface 1 with an angle of incidence greater than 16 is totally reflected. Improved directional efficiency is achieved by providing a reflector on the outer surface of curved surface 1 where radiation impinges at lesser angles.
In general less absorption of radiation occurs in N-type semiconductive materials, consequently it is preferred that the optical extraction structures formed in accord with this invention be of N-type conductivity material. Also, it is preferable that the impurity concentration be as small as is consistent with providing an acceptable junction, in order to reduce impurity absorption, even though this phenomenon is a secondary consideration.
While the light source of FIGURE 1 that employs a reflector structure offers optimum luminous efliciency and is therefore a preferred structure for use in the practice of my invention; my invention can also be used to great advantage with a structure as shown in FIGURE 2, that features a lens. More particularly, the optical structure of FIGURE 2 is oftentimes referred to as a Weierstrass sphere. As shown, a P-N junction is formed in a semiconductive crystal having a substantially spherical surface 11. Suitable electric contacts 12 and 13 are connected to the P and N portions, respectively, to provide electrical excitation of junction 10 from source 14. Radiation 15 is transmitted through the N-type conductivity material, impinges upon spherical surface 11 and is transmitted to an outer medium. Junction 10 is positioned reactive to spherical surface 11 so that all radiation impinges on surface 11 at an angle of incidence less than that at which total reflectivity occurs.
In accord with the present invention the semi-conductive material possesses a minimum band-gap in the vicinity of junction 10 and the band-gap is increased, preferably gradually, progressing through the body toward the left as viewed in FIGURE 2. The energy band-gap variation across the device of FIGURE 1 in a preferred embodiment is illustrated in FIGURE 3. The energy band-gap is minimum in the junction region 1' and increases therefrom in the main body of the crystal Thus, radiation originating in junction 10 is transmitted to spherical surface 11 with a minimum of absorption, resulting in optimum efliciency for the light source.
While only certain preferred features of the invention have been shown by way of illustration, many modificatrons and changes will occur to those skilled in the art. For example, while the present invention is primarily concerned w1th light sources, it is evident that the graded 'band-gap structures of this invention are equally applicable where radiation from an external source is to be focussed upon a P-N junction to provide, for example, a photocell. It is, therefore, to be understood that the appended claims are intended to cover this and all other such modifications and changes as fall within the true spirit and scope of my invention.
What I claim as new and desire to secure by Letters Patent of the United States is:
1. A light source comprising a crystalline semiconductive body constituted of an alloy semiconductive material; a PN junction in said body adapted to provide radiation in response to electrical excitation; the constituents of said alloy being present in the vicinity of said junction in concentrations that provide a predetermined band-gap energy in the vicinity of said junction; a portion of said body being adapted to transmit said radiation; said constituents being present in different concentrations in said substantially all of said body other than said junction to provide a band-gap energy therein which is greater in magnitude than said predetermined band-gap energy; and, means for providing said electrical excitation in a forward direction across said junction for producing radiation which is efficiently transmitted through said body.
2. The light source of claim 1 wherein the bandgap of said material increases gradually and substantially uniformly progressing in a direction perpendicular to and away from said junction.
3. The light source of claim 2 wherein said alloy semiconductive material is constituted essentially of a solid solution of gallium arsenide and gallium phosphide.
4. The light source of claim 3 wherein the composition of said semiconductive material in the vicinity of said junction includes more than 50 mole percent gallium arsenide, remainder consisting essentially of gallium phosphide; and, the concentration of gallium arsenide decreases and the concentration. of gallium phosphide increases progressing away from said junction,
5. A light source comprising: a semiconductive body constituted of at least two mutually soluble constituents selected from the group consisting of the lll-V and II-VI compounds; said constituents being present in said body in varying concentrations along at least one predetermined direction to provide a varying band-gap in said body along said direction; and, means for generating light radiation within said body in the region of lowest band p- References Cited by the Examiner UNITED STATES PATENTS 3,l32,057 5/1964 Greenberg l48-33.4
OTHER REFERENCES Applied Physics Letters, December 1, 1962, volume 1, Number 4, pages 82 and 83.
Holonyak et al.: Coherent (Visible) Light Emission From Ga (As P junctions.
JAMES W. LAWRENCE, Primary Examiner.
R. JUDD, Assistant Examiner.

Claims (1)

1. A LIGHT SOURCE COMPRISING A CRYSTALLINE SEMICONDUCTIVE BODY CONSITUTED OF AN ALOY SEMICONDUCTIVE MATERIAL; A P-N JUNCTION IN SAID BODY ADAPTED TO PROVIDE RADATION IN RESPONSE TO ELECTRICAL EXCIATION; THE CONSTITUENTS OF SAID ALLOY BEING PRESENT IN THE VICINITY OF SAID JUNCTION IN CONCENTRATIONS THAT PROVIDE A PREDETERMINED BAND-GAP ENERGY IN THE VICINITY OF SAID JUNCTION; A PORTION OF SAID BODY BEING ADAPTED TO TRANSMIT SAID RADIATION: SAID CONSTITUENTS BEING PRESENT IN DIFFERENT CONCENTRATIONS IN SAID SUBSTANTIALLY ALL OF SAID BODY OTHER THAN SAID JUNCTION TO PROVIDE A BAND-GAP ENERGY THERIN WHICH IS GREATER IN MAGNITUDE THAN SAID PREDETERMINED BAND-GAP ENERGY; AND, MEANS FOR PROVIDING SAID ELEC-F
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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3354342A (en) * 1964-02-24 1967-11-21 Burroughs Corp Solid state sub-miniature display apparatus
US3398310A (en) * 1965-03-11 1968-08-20 Hewlett Packard Co Indirect energy band gap topology injection electroluminescence source
US3428872A (en) * 1965-07-31 1969-02-18 Hitachi Ltd Body comprising a mark for indirect detection of an objective part and method of detecting the position of said objective part
US3454843A (en) * 1965-08-13 1969-07-08 Int Standard Electric Corp Modulating device having a curved p-n junction
US3462605A (en) * 1965-09-22 1969-08-19 Gen Electric Semiconductor light-emitter and combination light-emitter-photocell wherein the reflector of the light-emitter is comprised of a material different from that of the light-emitter
US3473067A (en) * 1966-02-23 1969-10-14 Siemens Ag Hemispherical luminescence diode producing a real image of the p-n junction
US3488234A (en) * 1963-07-17 1970-01-06 Philips Corp Semiconductor device
US3500135A (en) * 1965-09-28 1970-03-10 Chou H Li Surface-contoured,energy-transforming solid-state device
US3518418A (en) * 1966-12-21 1970-06-30 Philips Corp Electro-luminescent diode and radiation projector
US3518476A (en) * 1965-07-07 1970-06-30 Siemens Ag Luminescence diode with an aiiibv semiconductor monocrystal and an alloyed planar p-n junction
US3569997A (en) * 1967-07-13 1971-03-09 Inventors And Investors Inc Photoelectric microcircuit components monolythically integrated with zone plate optics
US3593055A (en) * 1969-04-16 1971-07-13 Bell Telephone Labor Inc Electro-luminescent device
US3748593A (en) * 1970-11-17 1973-07-24 Method and means of construction of a semiconductor material for use as a laser
US3763389A (en) * 1970-05-11 1973-10-02 P Schwarz Shadow mask having concave reflecting surface surrounding each aperture
US3996492A (en) * 1975-05-28 1976-12-07 International Business Machines Corporation Two-dimensional integrated injection laser array
US4082978A (en) * 1973-09-27 1978-04-04 Peter Schwarz Color television, having superimposed colors
US4094752A (en) * 1974-12-09 1978-06-13 U.S. Philips Corporation Method of manufacturing opto-electronic devices
US4126812A (en) * 1976-12-20 1978-11-21 Texas Instruments Incorporated Spherical light emitting diode element and character display with integral reflector

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3132057A (en) * 1959-01-29 1964-05-05 Raytheon Co Graded energy gap semiconductive device

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3132057A (en) * 1959-01-29 1964-05-05 Raytheon Co Graded energy gap semiconductive device

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3488234A (en) * 1963-07-17 1970-01-06 Philips Corp Semiconductor device
US3354342A (en) * 1964-02-24 1967-11-21 Burroughs Corp Solid state sub-miniature display apparatus
US3398310A (en) * 1965-03-11 1968-08-20 Hewlett Packard Co Indirect energy band gap topology injection electroluminescence source
US3518476A (en) * 1965-07-07 1970-06-30 Siemens Ag Luminescence diode with an aiiibv semiconductor monocrystal and an alloyed planar p-n junction
US3428872A (en) * 1965-07-31 1969-02-18 Hitachi Ltd Body comprising a mark for indirect detection of an objective part and method of detecting the position of said objective part
US3454843A (en) * 1965-08-13 1969-07-08 Int Standard Electric Corp Modulating device having a curved p-n junction
US3462605A (en) * 1965-09-22 1969-08-19 Gen Electric Semiconductor light-emitter and combination light-emitter-photocell wherein the reflector of the light-emitter is comprised of a material different from that of the light-emitter
US3500135A (en) * 1965-09-28 1970-03-10 Chou H Li Surface-contoured,energy-transforming solid-state device
US3473067A (en) * 1966-02-23 1969-10-14 Siemens Ag Hemispherical luminescence diode producing a real image of the p-n junction
US3518418A (en) * 1966-12-21 1970-06-30 Philips Corp Electro-luminescent diode and radiation projector
US3569997A (en) * 1967-07-13 1971-03-09 Inventors And Investors Inc Photoelectric microcircuit components monolythically integrated with zone plate optics
US3593055A (en) * 1969-04-16 1971-07-13 Bell Telephone Labor Inc Electro-luminescent device
US3763389A (en) * 1970-05-11 1973-10-02 P Schwarz Shadow mask having concave reflecting surface surrounding each aperture
US3748593A (en) * 1970-11-17 1973-07-24 Method and means of construction of a semiconductor material for use as a laser
US4082978A (en) * 1973-09-27 1978-04-04 Peter Schwarz Color television, having superimposed colors
US4094752A (en) * 1974-12-09 1978-06-13 U.S. Philips Corporation Method of manufacturing opto-electronic devices
US3996492A (en) * 1975-05-28 1976-12-07 International Business Machines Corporation Two-dimensional integrated injection laser array
US4126812A (en) * 1976-12-20 1978-11-21 Texas Instruments Incorporated Spherical light emitting diode element and character display with integral reflector

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