CA1214252A - Semiconductor electrodes having multicolor luminescence - Google Patents

Semiconductor electrodes having multicolor luminescence

Info

Publication number
CA1214252A
CA1214252A CA000450828A CA450828A CA1214252A CA 1214252 A CA1214252 A CA 1214252A CA 000450828 A CA000450828 A CA 000450828A CA 450828 A CA450828 A CA 450828A CA 1214252 A CA1214252 A CA 1214252A
Authority
CA
Canada
Prior art keywords
article
semiconductor
layer
semiconductors
semicon
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
Application number
CA000450828A
Other languages
French (fr)
Inventor
Arthur B. Ellis
Michael K. Carpenter
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.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
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 Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Application granted granted Critical
Publication of CA1214252A publication Critical patent/CA1214252A/en
Expired legal-status Critical Current

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Classifications

    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00Electroluminescent light sources
    • H05B33/12Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H05B33/145Arrangements of the electroluminescent material

Abstract

SEMICONDUCTOR ELECTRODES HAVING
MULTICOLOR LUMINESCENCE

Abstract of the disclosure A multicolor luminescent article comprises a layer of a first luminescent semiconductor having a discontinuous layer, pattern or image comprised of a second luminescent semiconductor on at least one surface whereof.

Description

SEMICONDUCTOR ELECTRODES HAVING
MULTICOLOR LUMINESCENCE

Technical Field This invention relates to semiconductor materials which exhibit photolurninescence.

_ckground of toe Art Electroluminescence occurs in semiconductor materials which are capable of emitting visible or near visible radiation when an electrical current passes through the semiconductor. Photo luminescence can also occur in these materials. If external light is used to excite the semiconductor while there is an applied voltage across the material, a characteristic wavelength of light is emitted. These characteristic wavelengths vary amongst different photo luminescent semiconductors and can be varied in a single semiconductor by doping the material. The Dupont will ordinarily cause a shift in the wavelength of radiation emitted by the material.
Amongst the various studies on the luminescence of photo-stimulated electroluminescent materials is "Luminescent Photoelectrochemical Cells", Streckert, H. H., Tong, JO and Ellis, A. B., J. Am. Chum. So., Vol. 104, No. 2, 1982, pi. 58l-588. To us note earn that the intensity of light emitted by electroluminescence varies directly with the applied voltage. The efficiency of charge transfer and good electrical contact at the surface is also noted as important in the efficiency of the process.

Summary of the Invention It has been found in the practice of the present invention that a multicolor electroluminescent :.''' article may be produced. The article must comprise a layer of a first electroluminescent semiconductor, and over only a portion of the surface of said layer a second electroluminescent semiconductor emitting a characteristic wavelength at least 50 no different from the characteristic wavelength of the first semiconductor.
According to the present invention there is provided a luminescent article comprising at least one layer of an electron luminescent or photo luminescent semiconductor and distributed over at least one surface of said layer a discontinuous second elector-luminescent or photo luminescent semiconductor having a character fistic emission differing by at least 50 no from the characteristic emission of said first semiconductor.

Detailed Description of the Invention Many different types of materials, both inorganic and organic in nature are known to electroluminesce. Amongst these materials are lanthanum oxysulfidel gadolinium oxybromides, gad-linium oxysulfide, lanthanum oxybromide, cadmium sulfide, cadmium solenoid, zinc oxide, zinc sulfide, zinc solenoid, cadmium tailored, poly-N-vinylcarbazole, substituted poly-N-vinylcarba-zones, bisbenzocarbazolephenylmethane and others. These materializer generally used as homogeneous layers or homogeneously dispersed layers. For example, commercial X-ray intensifying screens home-generously mix materials to alter the effective wavelength of radiation emitted.
The present invention provides a non-homogeneous - surface having a pattern-wise distribution of different electron luminescent semiconductors on that surface so that an image pattern is provided when the surface is caused to luminous The a-t least
- 2 -~Z~52 two electroluminescent semiconductors must have characteristic emissions which differ by at least 50 no to be distinguishable by the human eye. Preferably the emissions will differ by at least 100 no and more preferably by at least 200 no to effect good visual contrast.
The article providing this construction may be produced by any of a number of means. A first layer may be formed by conventional means such as coating of the semiconductor in a binder, thermal vapor deposition, sputtering, crystallization out G, :. . ':'; ' pa -of solution and the like. The second, pattern-distrikuted electroluminescent semiconductor may be deposited on the surface by any of -these molds, the pattern being formed by a number of alternative procedures.
The surface of the first semiconductor may be masked during -the deposition of the second photo conductor.
A continuous layer of the second semiconductor may be etched in a pattern using a resist layer. A pro-patterned, discontinuous electroluminescent layer also may be adhered to -the surface of the first semi-conductor. Each of these procedures is capable of providing a construction according to the present invention.
The article may also be constructed by etching an electroluminescent layer which does not contain distinct layers of different semiconductors, but rather has a graded zone of change between at least two different electroluminescent materials. By having a gradation of such materials, the amount of etching performed at any spot in the surface will control the wavelength of the emission from that spot. for example, first consider a cadmium solenoid substrate having sulfur diffused in through its surface -to a depth of about one micrometer. The surface will emit in the green from -the cadmium sulfide, but if the surface is progressively etched -to regions of increasing cadmium solenoid concentrations the Lowe emitted would pick up progressively more red until pure cadmium solenoid was reached and then only the characteristic red would be emitted. These graded articles may be provided by any procedure that is capable of providing the graded structure required. Various thermal vapor deposition and sputtering processes would be the best way of producing the structures. In particular, the process and apparatus described in US. Patent No.
4,364,995 would be particularly useful, with only minor changes needed in the materials provided in the coating procedure. For example, that apparatus I

uses a baffle to partially separate two vapor deposition streams. It one luminescent phoioconductor is provided on one side of the baffle and a sconce photocond-lct-or on the other, a graded intermediate zone can he provided.
The thickness of -the -total layer or individual ingredients is con-trolled by the amount of photo conductor evaporated.
The degree and rate of mixing in the graded zone is controlled by the extension of the baffle. Mixtures of three or more photo conductors can be made by adding a second baffle to the chamber. Extremely thin layers can be provided by these procedures and even tricolor emissions could be made in a 1-2 em layer.
The thickness of the various layers is no-t critical. The layers only need to be thick enough -to provide a sufficient intensity of emitted light upon excitation. If the emitted light is to be visible, a thickness of at least 0.01 micrometers for each layer is necessary. Preferably dimensions of at least 0.05, 0.10 or even 0 50 micrometers are desirable.
Greater thicknesses do not provide significantly better results. Thicknesses of 1 -to 10 microns work equally as well, but are more costly. With greater thicknesses of the top layer, particularly where etching is performed, increased production costs would also be encountered.
The voltage may be applied to the article of the present invention by any configuration which does not block the emission of light from the surface.
The article may be placed in an electrolyte solution with anodic and cathodic connections to the two surfaces of the article. A more convenient construction uses transparent conductive layers on both surfaces. Such layers could comprise -transparent conductive polymers, transparent conductive filled polymers, transparent metal films and the like. The transparency is, of course, necessary only on the emitting surface, and any conductive layer may be used on the back side of the article.
The graded construction can also provide particular advantages based on properties of graded substrates which may exhibit variable color emission depending upon the applied voltage. Such an article would have a luminescent layer comprising a first photo luminescent semiconductor having at least one material present in solid solution with said first semiconductor which alters the spectral luminescence of said first semiconductor, said material being selected from the group consisting of a Dupont for said first semiconductor having a spectral emission differing by at least 50 nanometers from the spectral emission of said first semiconductor, the concentration of said second component being greater at one surface of said layer than at the other surface, the concentration of said material varying with respect to the first semiconductor by at least 40% by weight through a thickness of 0.01 to l em from said one surface.
The semiconductor substrates which exhibit variable color emission in accordance with the present invention are preferably characterized as solid state solutions of three elements, including at least one metal and at least one non-metal element: these elements function in the electrode substrate as a constant element, a substituent element and a displaced element.
The concentration of the substi-tuent and the displaced elements, both of which are either metals or non-metals, is varied, preferably monotonically, with depth such that the band gap energy between the valence and conduction bands changes with depth. For emissions in the visible spectrum, assuming band edge emission, the band gap would preferably vary between about 1.7 eve and 3 eve Any combination of three metal and non-metal elements that form solid solutions together which satisfied the foregoing band gap energy requirements may be utilized in accordance with the present invention.
Examples of such trios of elements are: cadmium, I

selenium and sulfur; zinc, selenium and sulfur; cadmium, zinc and sulfur; and cadmium, selenium and zinc.
To the extent that such element; Stacy the EorccJoincJ
requirements of forming solid solutions a-t all levels of substitution and having appropriate band gap energies, any one of -the trio of elements may serve as the constant element the displaced emanate or -the substituent.
These and other aspects of the present invention can be seen in -the following non-limiting examples.
Example 1 us a specific illustrative example of a graded device formed in accordance with the invention, graded cadmium sulfide/cadmium solenoid (Cuds Sol I
0 X < 1) samples were prepared from 5 by 5 by 1 millimeter, vapor-grown, single-crystal c-plates ox n-type cadmium solenoid (resistivity approximately 2 ohm-cm; 4-point probe method). A Case plate was etched with Bra in methanol (1:10 V/V) and placed in a 6-millimeter inside diameter, 8-millimeter outside diameter quartz tube with approximately I milligrams of sulfur, which was free of metallic impurities -to better than 10 parts per million (Pam). The quartz ampule was evacuated (approximately 1 torn), sealed to a volume of about 2 cubic centimeters and placed in a preheated Lundberg furnace (700C) for 15 minutes.
After the ampule was removed from the furnace, one end was contacted by a heat sink to prevent the sulfur from condensing on the crystal substrate. The crystal substrate was then removed and placed in a similar tube with approximately 1 milligram of cadmium having less than 1 Pam of metallic impurities. The -tube was evacuated and sealed and again heated at 700C
for 15 minutes. After its removal prom the ampule, a yallium-itldium ohmic contact was formed on one surface of the substrate and a copper wire attached -to the contact with silver epoxy. The substrate was then encapsulated in epoxy, leaving one surface exposed, and mounted in an electrochemical cell containing f3 or an electrolyte, a platinum counter electrode, and an SUE reference electrode.
A polymeric resist layer in a recognizable pattern was painted on the surface of the layer having the diffused sulfur therein, and the exposed surface etched -to a depth sufficient to expose the pure cadmium solenoid. The resist was then dissolved from the surface.
The emission electrode with an etched, graded, substituted surface layer prepared as described above was incorporated in a cell with a platinum counterelec-trove and a SUE reference electrode and connected to a source of variable voltage potential. Aqueous alkaline polysulfide electrolyte (1 M OH /1 M so /0.1 M S) or aqueous alkaline peroxydisulfite, or aqueous alkaline sulfide (1 M OH /1 M so ) electrolyte could be used in the cell. The emission electrode had an exposed surface area of approximately 0.l5 square centimeter. To facilitate analysis of the emission spectra, the cell was constructed in the sample comport mint of an emission spectrometer. Front surface electroluminescence spectra were obtained. The electrolyte used was 1 M peroxydisulfate and was purged by bubbling No through i-t. visible ima~c could be visually observed in a reduced lighting background.
An image of rev on a green background was produced. By increasing the voltage, the field could be shifted within the article and the entire emission would appear to be green. Thus, the visible emission is changed from providing a visible pattern to providing only a continuous color by altering the voltage.

Claims (19)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A luminescent articla comprising at least one layer of an electroluminescent or photo-luminescent semiconductor and distributed over at least one surface of said layer a discontinuous second electroluminescent or photoluminescent semiconductor having a characteristic emission differing by at least 50 nm from the characteristic emission of said first semiconductor.
2. The article of claim 1 wherein both semiconductors are photoluminescent.
3. The article of claim 1 wherein both semiconductors are electroluminescent.
4. The article of claim 2 wherein both semiconductors are inorganic photoluminescent semicon-ductors.
5. The article of claim 3 wherein both semiconductors are organic electroluminescent semicon-ductors.
6. The article of claim 2 wherein both semiconductors are organic photoluminescent semicon-ductors.
7. The article of claim 3 wherein both semiconductors are inorganic electroluminescent semicon-ductors.
8. The article of claim 4 wherein one of the semiconductors is cadmium selenide.
9. The article of claim 7 wherein one of the semiconductors is cadmium selenide.
10. The article of claim 8 wherein at least one semiconductor is cadmium sulfide.
11. The article of claim 9 wherein at least one semiconductor is cadmium sulfide.
12. The article of claim 4 wherein conductive layers are present on both surfaces of said article, and the conductive layer over said discontinuous layer is transparent.
13. The article of claim 5 wherein conductive layers are present on both surfaces of said article, and the conductive layer over said discontinuous layer is transparent.
14. The article of claim 6 wherein conductive layers are present on both surfaces of said article, and the conductive layer over said discontinuous layer is transparent.
15. The article of claim 7 wherein conductive layers are present on both surfaces of said article, and the conductive layer over said discontinuous layer is transparent.
16. The article of claim 4 wherein there is a graded change in the composition of the discontinuous layer such that the concentration of the first semicon-ductor increases in the composition of the article when moving vertically from the discontinuous layer towards the first semiconductor.
17. The article of claim 5 wherein there is a graded change in the composition of the discontinuous layer such that the concentration of the first semicon-ductor increases in the composition of the article when moving vertically from the discontinuous layer towards the first semiconductor.
18. The article of claim 6 wherein there is a graded change in the composition of the discontinuous layer such that the concentration of the first semicon-ductor increases in the composition of the article when moving vertically from the discontinuous layer towards the first semiconductor.
19. The article of claim 7 wherein there is a graded change in the composition of the discontinuous layer such that the concentration of the first semicon-ductor increases in the composition of the article when moving vertically from the discontinuous layer towards the first semiconductor.
CA000450828A 1983-03-30 1984-03-29 Semiconductor electrodes having multicolor luminescence Expired CA1214252A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/480,471 US4780643A (en) 1983-03-30 1983-03-30 Semiconductor electrodes having multicolor luminescence
US480,471 1990-02-14

Publications (1)

Publication Number Publication Date
CA1214252A true CA1214252A (en) 1986-11-18

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US (1) US4780643A (en)
EP (1) EP0121405A3 (en)
JP (1) JPS59182584A (en)
CA (1) CA1214252A (en)

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US4645932A (en) * 1985-03-18 1987-02-24 Minnesota Mining And Manufacturing Company Diodes with chemically sensitive luminescence
US4851723A (en) * 1988-08-01 1989-07-25 Westinghouse Electric Corp. Coolant pump system for variable speed generators
FR2702870B1 (en) * 1993-03-19 1995-04-21 Thomson Csf Electroluminescent screen.
DE59713024D1 (en) 1996-06-26 2010-01-28 Osram Opto Semiconductors Gmbh Light-emitting semiconductor chip and light-emitting semiconductor component and method for its production
US6053795A (en) * 1998-01-13 2000-04-25 3M Innovative Properties Company Toy having image mode and changed image mode
US6120026A (en) * 1998-01-13 2000-09-19 3M Innovative Properties Co. Game with privacy material
US6160663A (en) * 1998-10-01 2000-12-12 3M Innovative Properties Company Film confined to a frame having relative anisotropic expansion characteristics
GB0011749D0 (en) * 2000-05-17 2000-07-05 Cambridge Display Tech Ltd Light-eminating devices
US7187885B2 (en) * 2004-10-29 2007-03-06 Samsung Electronics Co., Ltd. Oxidation of volatile organic compounds in electrographic printing
US9566758B2 (en) 2010-10-19 2017-02-14 Massachusetts Institute Of Technology Digital flexural materials
US9809001B2 (en) 2010-10-19 2017-11-07 Massachusetts Institute Of Technology Flexural digital material construction and transduction
US20140145522A1 (en) * 2011-11-04 2014-05-29 Massachusetts Institute Of Technology Electromagnetic Digital Materials
US9506485B2 (en) 2011-11-04 2016-11-29 Massachusetts Institute Of Technology Hierarchical functional digital materials
WO2013192599A1 (en) 2012-06-21 2013-12-27 Massachusetts Institute Of Technology Methods and apparatus for digital material skins

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US2921218A (en) * 1956-03-01 1960-01-12 Rca Corp Electroluminescent devices
US3153166A (en) * 1960-08-05 1964-10-13 Westinghouse Electric Corp Electroluminescent device having connections on the base
US3225253A (en) * 1961-12-28 1965-12-21 Ibm Electroluminescent photoconductive display device
US3648052A (en) * 1969-01-22 1972-03-07 Matsushita Electric Ind Co Ltd Solid-state image-converting device
US3783353A (en) * 1972-10-27 1974-01-01 Rca Corp Electroluminescent semiconductor device capable of emitting light of three different wavelengths
FR2248663B1 (en) * 1972-12-13 1978-08-11 Radiotechnique Compelec
US4211586A (en) * 1977-09-21 1980-07-08 International Business Machines Corporation Method of fabricating multicolor light emitting diode array utilizing stepped graded epitaxial layers
US4356429A (en) * 1980-07-17 1982-10-26 Eastman Kodak Company Organic electroluminescent cell
US4364995A (en) * 1981-02-04 1982-12-21 Minnesota Mining And Manufacturing Company Metal/metal oxide coatings
US4543511A (en) * 1983-03-24 1985-09-24 Wisconsin Alumni Research Foundation Semiconductor electrodes having regions of graded composition exhibiting photoluminescence and electroluminescence

Also Published As

Publication number Publication date
JPS59182584A (en) 1984-10-17
US4780643A (en) 1988-10-25
EP0121405A3 (en) 1986-07-16
EP0121405A2 (en) 1984-10-10

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