U.S. patent number 3,889,016 [Application Number 05/257,347] was granted by the patent office on 1975-06-10 for method of making a direct current electroluminescent device.
Invention is credited to Alla Nikolaevna Gergel, Andrei Antonovich Shkola, Natalya Andreevna Vlasenko.
United States Patent |
3,889,016 |
Vlasenko , et al. |
June 10, 1975 |
METHOD OF MAKING A DIRECT CURRENT ELECTROLUMINESCENT DEVICE
Abstract
A method of making a direct-current electroluminescent device in
which an electroluminescent film is deposited onto a heated
substrate coated with an optically transparent electrode by means
of vacuum evaporation of a first substance comprising zinc sulphide
doped with Mn, Cu and Cl and a second substance comprising metallic
zinc in a quasi-closed volume, both substances being evaporated
simultaneously and each substance being evaporated from a separate
evaporator. The temperature of the evaporator containing the first
substance comprising zinc sulphide doped with Mn, Cu and Cl is
maintained within a range enabling the first substance to evaporate
at a specified rate, while the temperature of the separate
evaporator containing the second substance of metallic zinc is
maintained within a range enabling the second substance to
evaporate at a specified rate, thereby enabling the desired
concentration of zinc to be deposited onto said film. A metal
electrode is deposited onto the obtained film by means of vacuum
evaporation.
Inventors: |
Vlasenko; Natalya Andreevna
(Kiev, SU), Gergel; Alla Nikolaevna (Kiev,
SU), Shkola; Andrei Antonovich (Kievskaya Oblast,
SU) |
Family
ID: |
22975941 |
Appl.
No.: |
05/257,347 |
Filed: |
May 26, 1972 |
Current U.S.
Class: |
427/66 |
Current CPC
Class: |
H05B
33/10 (20130101) |
Current International
Class: |
H05B
33/10 (20060101); B44d 001/18 (); B44d
001/16 () |
Field of
Search: |
;117/16R,107,217,227,201 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Weiffenbach; Cameron K.
Claims
We claim:
1. A method of making a direct-current electroluminescent device,
in which an electroluminescent film is deposited onto a heated
substrate covered with an optically transparent electrode,
comprising vacuum evaporating zinc sulphide doped with manganese,
copper, and chlorine from a first evaporator at a temperature
between 1,050.degree.C-1,250.degree.C and simultaneously vacuum
evaporating metallic zinc from a second evaporator at a temperature
between 360.degree.C-400.degree.C, thereby enabling the desired
concentration of zinc to be obtained in said film; and vacuum
evaporating a metal onto said film to form an electrode on said
film.
2. A method of making a direct-current electroluminescent device
according to claim 2, wherein said first and second substances are
evaporated in separate evaporators contained in a quasi-closed
volume having said substrate at the upper end thereof and said
evaporators at the lower end thereof, thereby enabling an excess of
zinc of a predetermined concentration to be uniformly distributed
throughout the entire thickness of said film.
3. A method of making a direct-current electroluminescent device
according to claim 3, wherein the temperature of said substrate is
maintained between 250.degree.-300.degree.C.
Description
The present invention relates to methods of manufacture of
electroluminescent devices and, more particularly, to methods of
making direct-current electroluminescent devices utilized in
optoelectronics, automatic systems, and computers.
Known in the art is a method of making a direct-current
electroluminescent device.
According to the known method, the electroluminescent devices are
manufactured by (1) depositing an electroluminescent film onto a
substrate heated to a temperature of 290.degree.-500.degree.C,
which substrate is coated with a layer of SnO.sub.2 (optically
transparent electrode), by means of vacuum evaporation of zinc
sulphide doped with manganese; and then (2) depositing a metal
electrode onto the obtained film by means of vacuum evaporation.
The evaporated substance is usually either in the form of (1) a
powdery ZnS doped with Mn forming an excess of Zn obtained by
firing a mechanical mixture of ZnS and metallic manganese in a flow
of nitrogen at 1,110.degree.C during 3 hours, and then adding 1% of
metallic zinc to the powder after the firing, or (2) crystals of
ZnS doped with Mn grown from a melt and containing excessive
zinc.
In such films the electroluminophore is not uniformly doped with
zinc throughout the film thickness. This is explained by the fact
that Zn and ZnS have different evaporation temperatures
(400.degree. and 1,100.degree.C, respectively), and that during the
evaporation of a mixture of these substances from a single
evaporator the first portions of the evaporated substance contain
mainly zinc, while the last portions thereof contain substantially
ZnS. The non-uniform distribution of zinc throughout the thickness
of the film and its uncontrollable content in the film-as in the
case of evaporating crystals or a powdery, mechanical mixture of
ZnS doped with Mn and Zn-are responsible for the uncontrollable and
poor reproducible properties of the film.
The electroluminescent films obtained by means of the known method
feature extremely low brightness (10.sup.-.sup.8 foot-lamberts 3.5
10.sup.-.sup.8 nits) even at a considerable voltage (up to 100
volts), and, therefore, as a practical matter, they cannot be used
in the manufacture of electroluminescent devices.
In addition, the known method is disadvantageous in that production
costs are higher because a number of labor consuming operations are
necessary to make the material to be evaporated. Moreover, the
present method permits the temperature of the substrate to be
reduced from 290.degree.-500.degree.C to
250.degree.-300.degree.C.
An object of the present invention is to provide a method of making
a direct-current electrolumiscent device which allows one to
increase the reproducibility of the parameters of the manufactured
devices, to increase the brightness thereof, and to increase the
life of the electroluminescent devices within the range of rated
brightness (.about.20 nits).
This object is attained by the present invention, which provides a
method of making a direct-current electroluminescent device in
which, zinc sulphide doped with Mn, Cu and Cl and metallic zinc are
simultaneously evaporated in a quasi-closed volume, each substance
being evaporated from a separate evaporator, whereby the
temperature of the evaporator in which the zinc sulphide doped with
Mn, Cu and Cl is contained is maintained within that range
commensurate with the specified rate desired of this substance,
while the temperature of the evaporator in which the metallic zinc
is contained is maintained within that range required to provide a
predetermined concentration of zinc in the luminophore film.
Thus, according to a preferred embodiment of the present invention,
an electroluminescent film is deposited by means of vacuum
evaporation -- onto a heated, 250.degree.-300.degree.C substrate
covered with a conductive layer and disposed in a quasi-closed
volume -- of vaporous:zinc sulphide doped with manganese, copper,
and chlorine from an evaporator, or of a previously prepared
powdery electroluminophore of like composition, and,
simultaneously, of vaporous zinc evaporated from another evaporator
separate from that in which the ZnS doped with Mn, Cu, and Cl are
evaporated.
The temperature of the evaporator containing the zinc sulphide
doped with Mn, Cu and Cl is preferably kept within the range of
1,050.degree.-1,250.degree.C while the temperature of the
evaporator containing the metallic zinc is kept within the range of
360.degree.-400.degree.C.
The proposed method of making a direct-current electroluminescent
device is advantageous in that it makes it possible to increase the
reproducibility of the parameters of the devices, as well as their
life (to 400-600 hours at a constant voltage), and to intensify the
brightness of the device for more than nine orders of magnitude at
an operating voltage not exceeding 20 volts.
The proposed method consists substantially of depositing a
luminophore film with excessive zinc by simultaneously evaporating,
under vacuum, a powdery luminophorescent substance comprising ZnS
doped with Mn, Cu, and Cl, and metallic zinc substance, each
substance being evaporated from a separate evaporator.
The entire process of evaporation is carried out in a quasi-closed
volume, i.e. in a vacuum device containing a vertical tubular
furnace with a closed upper end arranged under the cap of this
device and accommodating the substrate to be processed, the
evaporators being mounted at the lower end of the furnace.
The temperature of the evaporator containing the zinc sulphide
doped with manganese, copper and zinc chloride is maintained within
the range of 1,050.degree.-1,250.degree.C, thereby providing for a
specified rate of evaporation of this substance, whereas the
temperature of the evaporator containing the metallic zinc is
maintained within the range of 360.degree.-400.degree.C to provide
for a predetermined concentration of zinc in the electroluminophore
film.
The evaporation of zinc from a separate evaporator under the
correct conditions of evaporation makes it possible to obtain a
constant predetermined ratio of the rates of evaporation of ZnS
doped with Mn, Cu and Cl, and Zn, thereby enabling one to obtain
uniform doping of the electroluminophore film with zinc throughout
the entire volume of this film to ensure a specified concentration
of zinc in said film, and to increase the reproducibility of the
method. The use of the quasi-closed volume improves the conditions
of growth of the film, the reproducibility of the results, and
reduces the consumption of the substance, since the rate of
condensation of ZnS is increased due to the low rate of evaporation
of the particles from the heated substrate.
Given below is an example of carrying the proposed method into
effect.
EXAMPLE
A substrate with an optically transparent, current-conducting layer
of SnO.sub.2 is purified in a glow discharge and is heated to
250.degree.-300.degree.C in a tubular furnace under a vacuum of
2.10.sup.-.sup.5 mm Hg. The tubular furnace is equipped with
several evaporators having a flap placed between them and the
substrate. When the flap is closed, the powdery luminophore
comprising ZnS doped with Mn, Cu, and Cl is degassed by smoothly
increasing the temperature of the evaporator with said powdery
luminophore to 1,050.degree.C. Then the temperature of another
separate evaporator with metallic zinc therein is raised to
360.degree.-400.degree.C, and the flap is opened. The zinc is
evaporated from a quartz crucible having a heater with a heating
element of tungsten. In the process of evaporation the temperature
of the evaporator with containing the powdery luminophore
comprising ZnS doped with Mn, Cu, and Cl is raised from
1,050.degree. to 1,250.degree.C, while the rate of evaporation of
the ZnS doped with Mn, Cu, and Cl is maintained approximately
constant and equal to 0.5 to 0.6 microns per minute.
The temperature of the evaporator containing the metallic zinc
during the entire cycle of evaporation is kept constant and equal
to 360.degree.-400.degree.C.
The evaporation is maintained until the thickness of the
electroluminophore layer reaches 10 microns. After this the
evaporator and the furnace are de-energized. The obtained film is
cooled down in a vacuum. A metal electrode is deposited onto the
cooled film by means of vacuum evaporation.
The specimens obtained by the proposed method radiate yellow-orange
light with maximum intensity within the region of 585 nm when
applying a negative voltage on the metal electrode. A brightness of
20-30 nits is obtained at a voltage of 15-20 volts and a current
density of 0.6-1.0 mA/mm.sup.2. The life (the time of half-decay of
the brightness from the initial level of 20 nits) is equal to
1,000-2,000 hours at a slight increase in the applied voltage
during the process of operation (by 25-30%). The life of the
direct-current luminescent devices obtained by the present method
is considerably higher than that of the direct-current luminescent
devices obtained by any known method.
* * * * *