U.S. patent number 3,621,321 [Application Number 04/871,847] was granted by the patent office on 1971-11-16 for electroluminescent device with light emitting aromatic, hydrocarbon material.
This patent grant is currently assigned to Canadian Patents and Development Limited. Invention is credited to Digby F. Williams, Martin Schadt, Vanier City.
United States Patent |
3,621,321 |
|
November 16, 1971 |
ELECTROLUMINESCENT DEVICE WITH LIGHT EMITTING AROMATIC, HYDROCARBON
MATERIAL
Abstract
A thin body of active material in the form of anthracene or
naphthalene generates light when a current is passed through it by
the injection of electrons from an electrode containing negative
ions of a similar material e.g. anthracene, naphthalene or
tetracene) to a base electrode to which an external positive
potential relative to the electron-injecting electrode is applied.
The base electrode may be solid and transparent for transmission of
light generated in the active material or at its interface with the
base electrode. This device also acts as a rectifier, since
virtually no current will flow if the externally applied potential
is reversed.
Inventors: |
Digby F. Williams (Ottawa,
CA), Martin Schadt, Vanier City (Ontario, CA) |
Assignee: |
Canadian Patents and Development
Limited (Ottawa, Ontario)
|
Family
ID: |
25358278 |
Appl.
No.: |
04/871,847 |
Filed: |
October 28, 1969 |
Current U.S.
Class: |
313/504; 257/99;
257/100; 257/103; 257/632 |
Current CPC
Class: |
H05B
33/26 (20130101); H05B 33/145 (20130101) |
Current International
Class: |
H05B
33/26 (20060101); H05B 33/14 (20060101); H05b
033/02 (); H05b 033/26 () |
Field of
Search: |
;313/108R,108A,108D,358
;317/235 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
H Inokuchi et al., "The Photovoltaic Behaviors of Aromatic .
Hydrocarbons," Electrical Conductivity in Organic Solids, pp.
69-75, .
1961..
|
Primary Examiner: Roy Lake
Assistant Examiner: Palmer C. Demeo
Attorney, Agent or Firm: Stevens, Davis, Miller &
Mosher
Claims
1. An electroluminescent device comprising: a. a thin body of
light-generating, aromatic, electrically nonconducting, hydrocarbon
material, b. a first solid phase electrode having an electrically
conducting surface contacting a first surface of said
light-generating material, c. a second solid phase electrode
contacting a second surface of said light-generating material, said
second electrode containing negative ions of an aromatic
hydrocarbon material capable of injecting electrons into said
second surface upon the application of a negative potential to said
second electrode relative to a potential applied to said
electrically conducting surface of the first electrode, and d. at
least one of said electrodes being transparent for the transmission
therethrough of light generated in said light-generating material
by
2. A device according to claim 1, wherein said light-generating
material is anthracene and said second electrode includes negative
anthracene ions.
3. A device according to claim 1, wherein said light-generating
material naphthalene and said second electrode includes negative
naphthalene ions.
4. A device according to claim 1, wherein said light-generating
material is anthracene and said second electrode includes negative
naphthalene ions.
5. A device according to claim 1, wherein said light-generating
material is
6. A device according to claim 1, wherein said first electrode is
formed of electrically conducting glass.
Description
This invention relates to electroluminescent devices.
Electroluminescence over a considerable wavelength region is
possible using inorganic semiconductor systems. However, at least
as versatile in this respect are system using organic materials as
the active elements. Such organic materials are normally highly
electrically nonconducting, however, so that before
electroluminescence can be achieved it is necessary to find the
correct conditions for injecting electric charges (electrons or
holes) into the materials.
While, as indicated below, the present invention is not restricted
in its broad scope to the injection of charges into any one or two
particular materials, it will be convenient to take as typical
materials anthracene and naphthalene, whether in the form of single
crystals or as powder or in a matrix.
Injection of electric charge carriers into such materials has been
achieved using liquid electrodes. See for example H. Kallman et
al., J. Chem. Phys., 32,300 (1960); M. Pope et al., J. Chem. Phys.,
Vol. 36, No. 9, May 1, 1962, pages 2486 et seq.; and W. Helfrich et
al. U.S. Pat. No. 3,457,153 issued July 22, 1969 . Only in the
latter reference were sufficient currents reported to generate any
observable luminescence. Emission from an anthracene crystal
occurred primarily in the blue spectral region, and is believed to
have been generated by the direct recombination in the body of the
crystal of electrons and holes injected from the opposite faces of
the crystal by the respective liquid electrodes.
These liquid electrodes are, however, opaque and it has been
necessary to remove the light from the system through the edges of
the active crystals. This is inconvenient and relatively
inefficient, especially since for best performance the crystal will
normally be made as a very thin wafer, the liquid electrodes
obscuring most or all of the flat faces. Also only relatively short
term stability was available due to dissolving the active material
in the electrode solutions.
The principal objects of the present invention are to provide a
method of injecting carriers into such materials by means of
electrodes at least one of which is a transparent solid through
which the light generated in the active material can readily
emerge, and to give long-term stability to the system.
Another object is to obtain more light than has previously been
possible with devices of this type of comparable size and under
comparable operating conditions.
Yet another object is to produce a device that will act as a
rectifier as well as to produce light.
The present invention consists of an electroluminescent device
comprising: a. a thin body of light-generating, aromatic,
electrically nonconducting, hydrocarbon material, b. a first
electrode having an electrically conducting surface contacting a
first surface of said light-generating material, and c. a second
electrode contacting a second surface of said light-generating
material, said second electrode containing negative ions of an
aromatic hydrocarbon material capable of injecting electrons into
said second surface upon the application of a negative potential to
said second electrode relative to a potential applied to said
electrically conducting surface of the first electrode; d. at least
one of the said electrodes being in solid phase and transparent for
the transmission therethrough of light generated in said
light-generating material by recombination of said injected
electrons with holes.
The single figure of the accompanying drawing shows
diagrammatically and by way of example a cross section of one
device constructed in accordance with the present invention.
This device comprises a base 10 of conducting glass; then a layer
11 of the active material; then a layer of negative electrode
material 12 held within a glass-retaining ring 13, if necessary;
and finally a body of encapsulating wax 14. Leads 15 and 16 connect
to external terminals to which either relative positive or negative
direct voltage is applied as illustrated. That is the glass 10 will
always be positive relatively to the electrode 12, the potential of
these parts relative to ground being unimportant.
The base 10 is of glass, at least the upper surface of which has
been made conducting by one of the known surface treatment methods,
to form a first electrode. Alternatively, this conducting glass
surface electrode can be replaced by silver or gold paste. However,
since these materials are opaque, they would have to be constructed
with windows to permit the light emission.
The light-generating active material 11 should be kept as thin as
possible, since the light generated is proportional to the current,
and the current is proportional to the square of the voltage and
inversely as the cube of the thickness of the material. A thickness
of the order of 1 to 200 microns is preferred. This active material
may take the form of a crystal or may be in powder or other form.
For example, the following materials have been used satisfactorily
as the active material:-- a. Anthracene sublimation flakes. b.
Anthracene melt grown single crystals. c. Anthracene powder. d.
Anthracene powder in a matrix of methyl methoxylate plastic. e.
Naphthalene sublimation flakes.
The chemical form should be of high purity for maximum emission
intensity, and, although anthrancene and naphthalene have been
taken as the most convenient and readily available substances, the
active material can theoretically be any aromatic hydrocarbon in a
relatively pure chemical form. In practice, however, only those
materials having a high quantum efficiency of fluorescence can be
used with advantage.
The electrode material 12 will preferably consist of solid material
made by evaporation from a solution containing negative ions of a
hydrocarbon similar to that used as the active material. For
example, if the active material 11 is anthracene, the electrode
material 12 can be the evaporation product of anthracene dissolved
in a solvent such as will produce stable negative anthracene ions,
e.g. tetrahydrofuran, dimethoxyethane, dimethyl sulfoxide or
dimethyl formamide. The material can be prepared by interacting the
solution with metallic sodium or other alkali metal, care being
taken to keep the material under an inert atmosphere such as
nitrogen during production. Direct production of this electrode
material 12 by reduction of the active material 11 at its surface
is also possible by sublimation of the reductant, e.g. sodium
metal.
If the active material 11 is naphthalene, the electrode material 12
can likewise be a similar evaporated product of a negative ion
producing solution of naphthalene. While it is convenient to use
the same hydrocarbon for both materials this is not essential. For
example, the electrode material 12 can be naphthalene or tetracene
while the active material 11 is anthracene.
The retaining ring 13 is solely physical in function and will be
unnecessary if the electrode material 12 is deposited upon the
light-emitting material surface by other techniques, e.g.
sublimation. The wax 14 can be replaced by any other inert
substance or means for preventing access of air.
Upon application of the relative voltages shown, light is emitted
downwardly either through the glass base 10 or upwardly through the
electrode material 12 and wax 14, if these are sufficiently
transparent, or in both directions. There will also be emission
from the edges of the active material 11 unless this is
deliberately discouraged by some opaque material. The wavelength of
the emitted light may be varied by the choice of hydrocarbon for
the active material. Naphthalene will emit in the ultraviolet range
mainly from approximately 3500 to 4000A., and anthracene in the
blue range mainly from approximately 4100 to 4500A. Wavelength
changes can be achieved by doping. For example, anthracene doped
with one part per million of tetracene gives a green-blue emission
at approximately 4800-5000A. It has also been found that color
variations can be obtained by varying the voltage or the dopant
concentration.
If the externally applied potential is reserved, virtually no
current flows, so that the device acts as a rectifier. The forward
and reverse current ratio is of the order of 10.sup.5.
Under the condition of flow of injected electrons from the second
electrode 12 to the first electrode 10 the latter must be able to
supply sufficient holes to recombine with a sufficient number of
electrons to produce the required intensity of electroluminescence.
Many electrode materials satisfy this criteria, for example
conducting glass, silver paste and gold paste. If there is
substituted a solid substance capable of injecting holes into the
lower surface of the active material 11, for example anthracene
positive ions or naphthalene positive ions, a current will flow,
light will be generated, and also a rectifying action will be
observed. The positive ion electrodes, however, are opaque and only
permit light emitted from the sides of the device to be
observed.
* * * * *