Vol. 99, No.
~ GROWTH OF LUMINESCENCE
G R O W T H OF THE LUMINESCENCE SECTION
Rudolph Nagy*
During the last fifty years the members of The Electro-
chemical Society played a major role in the field of lighting.
When we consider that electrochemistry is the science which
deals with the physical and chemical changes produced by
the electric current, it becomes immediately apparent why
the electrochemist interests himself in converting electrical
energy into light. The numerous papers presented before the
Society or published in the JOURNALwill attest to this fact.
A brief survey of these papers is very revealing as to the fore-
sight of the founders of the Society. Of special interest, is the
paper of Hammer in 1903 (1) wherein many different methods
of prcducing light were shown before the Society. As an ex-
ample, Hammer demonstrated an early Edison "X-ray Lamp"
which in reality was a granddaddy of our present cathode
ray tube. Various phosphors such as calcium tungstate, zinc
sulfide, and zinc silicate were bombarded by an electron beam
to produce light. Various organic and inorganic luminescent
materials were also shown which were similar, if not identical,
to the ones used in many of our present-day advertising signs.
Hammer also demonstrated an early Cooper-Hewitt mercury
arc lamp enclosed in a screen soaked in rhodomin which was
a forerunner of the present color-corrected mercury lamp using
the high temperature germanate phosphor. Although the
first observations of luminescence have been credited to
Casciarlo, a Bologna shoemaker in 1602, synthetic phosphors
at the turn of the present century remained a scientific curi-
osity. It was not until the development of the fluorescent
lamp and the television tube that phosphors have become
common place.
During the past fifty years, papers dealing with mercury
and various metallic vapor arcs, suitable for lighting purposes
were presented. As early as 1905, Weintraub (2) discussed the
conductivity of metallic vapors for the purpose of producing
light. To indicate the progress of more recent years in this
field, Marden, Meister, and Beese (3) described high intensity
mercury arcs operating nearly up to one thousand atmospheres
and with efficiencies of over fifty lumens per watt.
Lamps producing ultraviolet radiations and their applica-
tion have always been of considerable interest to the elec-
trochemist. As an example, Baskerville (4) in 1906 had a very
interesting article on the use of ultraviolet radiations in study-
ing the fluorescence of some thirteen thousand minerals and
compounds. In 1940 Knowles and Reuter (5) reported on an
ultraviolet lamp used in destroying various mold, yeast,
and bacteria. This is only one of the many papers of a bio-
logical nature found in the JOURNAL. In 1937 the Society
conducted a symposium on Electrochemical Methods in
Biology. A review of various methods was presented by the
outstanding plant physiologist, Osterhout (6). Other authors
discussed the use of the dropping mercury electrode, glass
electrodes, and photoelectric devices as used in biology. In
1941 Klatt, et al. (7) had an interesting paper on the use of
the dropping electrode in the diagnosis of cancer.
Various instruments and their uses have always interested
the electrochemist, as is evidenced by the numerous papers on
* Research Department, Westinghouse Electric Corporation,
Bloomfield, New Jersey.
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SECTION 81C
instrumentation. As an example, Zworykin (8) was invited in
1941 to speak before the Society on the electron microscope.
This tool has proved to be useful in many electrochemical
processes. One of these is reported by Mrgudich and Clock
(9, 10) on x-ray and electron microscope studies of carbon
black. This instrument has also been extensively used in the
study of various phosphors. The x-ray diffraction apparatus
has been used on such diverse materials as phosphors by
Fonda and Froelich (11), silicon monoxide films by Braumann
(12), and rectifying selenium films by Clark and Roach (13).
It has in reality become a standard tool in most laboratories.
Other instruments such as automatic temperature controls
described by Fogle (14) or pH controls described by Greer
and Chalpin (15) which were nonexistent at the turn of the
century have become commonplace in industry today. Va-
rious types of photocells as described by Fink, et al. (16, 17)
and later by Rentschler and Henry (18) have become useful
tools. The electrochemist has contributed to the knowledge
of instrumentation and has taken advantage of new tools
developed in other fields.
Throughout the history of the Society, various theoretical
aspects of gaseous conduction were discussed. As early as
1903, Parsons (19) described electron conduction in vacuum
tubes. In 1923, Lind (20) directed a symposium on the elec-
trochemistry of gaseous conduction. A total of sixteen papers
was presented by such outstanding scientists as F. H. New-
man, S. Dushman, K. T. Compton, and many others. In
1936, Darrow (21) presented an informative lecture on elec-
tricity in gases. Gaseous conduction in lamps was also dis-
cussed by Buttolph (22) and van der Werfhorst (23). Papers
of this nature were setting the stage for the fluorescent lamp
which appeared on the scene in 1938.
However, before the world was ready for the fluorescent
lamp, considerable progress was reported to the Society on
incandescent lamp sources. As early as 1905, Roeber (24)
demonstrated the first tantalum, osmium, and graphitized
carbon lamps to be shown in this country. Bancroft (25) in
1908 discussed the various aspects of the electrochemistry
of light and Ives (26) in 1915 presented a paper on the con-
ception of an ideal light. Most of the early lighting engineers
were mainly concerned with the development of filaments
capable of operating at high temperatures.
It was not until 1939 that Marden (27) demonstrated be-
fore the Society various fluorescent materials and talked on
the new fluorescent lamp, pointing out that the art of con-
verting electrical energy into light had passed another mile-
stone. Before the conclusion of this meeting various members
of the Electronics Division organized a Lmninescence sub-
section which was to present periodic symposia on lumines-
cence.
The first Society Luminescence Symposium was held in
1945, at which time eight papers on phosphors and fluores-
cent lamps were presented. The symposium was a success.
Thayer (28) gave an informative paper on the quantum effi-
ciency of fluorescent lamps. His calculations indicated that
the fluorescent lamp with zinc beryllium phosphor has a
quantum efficiency of ninety per cent. Kenty and Cooper
 82C JOURNAL OF THE
Sylvania Electric Products Inc.
FIG. 1. Inspection of glass tubes used in fluorescent lamps
(29) showed the effect of various common gas impurities on
the output and operation of the fluorescent lamp. Such gases
as oxygen, carbon dioxide, and water, vapor react with mer-
cury to give a black mercury oxide that greatly decreases
light output.
At the next lmninescence meeting which was held in Louis-
ville in i947, Froelieh (30) presented a paper on a new ul-
traviolet phosphor, making it possible for the first time to
make an efficient fluorescent sunlamp. Butler (31) also pre-
sented one of a series of papers on barimn silicate phosphors,
some of which proved useful as "black-light" phosphors.
Of considerable interest was the paper of Bramley (32) on
aluminum-backed phosphor screens in cathode ray tubes. These
tubes can be operated at a higher voltage, have a higher out-
put, anti the aluminum reduces the tendency of phosphor
deterioration. The postwar years stinmlated considerable
demand for fluorescent lamps and television tubes. A tremen-
dous amount of energy was expended in research on new and
better phosphors and their application. Most of the scientific
papers that have resulted from such research, have been
presented at the Luminescence Symposia. Their number has
increased phenomenally.
In 1948 Froelich (33) reported on a new calcium silicate
phosphor which at present is used in many color corrected
fluorescent lamps. Smith (34) showed the importance of at-
mosphere on the firing of zinc sulfide phosphors. This paper
and those of Kroeger (35) show the sulfide phosphors are
much more complex in their constitution than was realized
by Lenard at the turn of the century. This is also exemplified
by the paper of Ward (36) who reported on the doubly acti-
vated alkaline earth sulfides. The energy stored by the phos-
phor as a result of ultraviolet excitation is released upon infra-
red excitation. The emission spectrum is governed by one of
the activators while the infrared excitation spectrum is
governed by the other impurity.
In 1949 a total of twenty-six papers dealing with all phases
of luminescence was published in the JOURNAL. I t would be
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ELECTROCHEMICAL SOCIETY A p r i l 1952
b w o n d the scope of this brief summaD , to comment on all
of the various papers. This was very ably done by Fondu (37)
in his review of articles on luminescence for 1949. Of special
interest was the paper of Jenkins, et al. (38), on alkaline earth
halnphosphates. These phosphors have completely replaced
the zinc ber.vllium silicates used in fluorescent lamps up to
this date. A number of papers on the mechanism of lumines-
cence have also been presented. Both Kroeger (39) and Smith
(40) reported that a part of the flux used in the formation of
sulfide phosphors may become an essential ingredient of the
phosphor. Garlich (41) working on the thermoluminescence
of phosphors was able to correlate the effect of constitution
and activator upon the trap depths of zinc sulfide phosphors.
The advancement in the art of cathode ray tube manufacture
can best be exemplified by the article of Sedowsky (42). He
described all of the then available methods of screen applica-
tion. Two years later, eleven papers dealing with various
phases of this subject were discussed before the newly formed
Screen Application section. This is a very good example of
the phenomenal growth of certain phases of science and the
ability of the Society to meet the needs of its members.
A summary of lmnineseence for the year 1950 was also
compiled by Fondu (43). Of the many new phosphors reported,
CaO-5IgO. 2SiO~ :Ti discovered by Smith (44) is of interest
because of its high efficiency under cathode ray bombardment
and since it contains titanium as an activator. Most of the
silicates in the past have been activated with manganese.
In calcium zinc silicate activated with thallium, Nagy, et al.
(45) found the addition of zinc to shift the emission spectrum
to the shorter wavelength. At the Washington meeting in
~) General Electric Company
FIG. 2. Factory sc'moning of glass tubes
1951, a large number of interesting new phosphors were de-
scribed. Of note was barium titanium phosphate of Hender-
son and Ranby (46) which contained thirty mole per cent
titanium oxide. This phosphor has an output and spectral
distribution very similar to magnesium tungstate. Prener
(47) showed that an efficient zinc sulfide phosphor can be
made using arsenic as an activator. Froelich, et al. (48) spoke
on a red emitting calcium phosphate activated with cerium
and manganese. He also discovered that a small per cent of
potassium or sodium greatly increased the stability and tem-
perature dependence of this phosphor. Another red phosphor,
zinc phosphate activated with manganese, was reported by
Snfith (49). X-ray diffraction patterns showed this phosphor
to exist in different forms depending upon the temperature of
heating and manganese concentration. Payne, et al. (50)
showed the direct excitation of phosphors by electric fields.
This principle first demonstrated by Destriau in 1937 is very
intriguing both from the theoretical as well as practical stand-
point. If more efficient phosphors can be found, this may prove
to be our mode of lighting in the future.
 Vol. 99, No. 4 GROWTH OF LUMINESCENCE SECTION 83C

lamps are exhausted while hot. Fig. 2 shows the factory sea-
soning of tubes prior to packing for shipment.
Fig. 3 and 4 pictorially show some of the processes employed
in producing television tubes. Luminescent materials are now
produced synthetically in relatively large quantities. The
"picture face" is put on television cathode ray tubes by a
settling process. This must be done under conditions free of
vibration (Fig. 3). A conductive coating is also put on the
inside of the tube to trap secondary electrons that bounce
off the fluorescent screen (Fig. 4). Following this, the emitting
cathode and control electrodes are sealed. As with fluorescent
lamps, television tubes are carefully seasoned and tested
prior to packing and shipping. Fig. 5 indic'ttes some of the
research necessary for such development. Here the spectral
distribution of light emitted by phosphors is being measm'ed.

9 Radio Corporationof America REFERENCES

FXG. 3. Putting "picture face" on television cathode ray
tubes by a settling process.
This brief survey depicting the role that The Electrochemical
Society played in the advancement of the science of lighting
and associated arts for the p'~st rift)" years does not claim to
be a review of literature of the subject. Rather it was written
to show the phenomenal progress made in this field by high-
lighting a few of the contributions made bv its members. In
addition to those mentioned, there are many papers of im-
portance throughout the JOURNAL and another writer could
have easily made another list of names of authors as imposing
as the one presented. The phenomenal growth during the past
few years clearly indicates the trend of the increasing stature
of the Society. Our knowledge, especially of phosl)hors, is
still in its infancy. There is a great deal to be learned regard-
ing the mechanisms of luminescence. We are in need of better
phosphors for fluorescent lamps, television tubes, and more
efficient high temperature and ultraviolet emitting 1)hosphors.
I t is predicted that ninny of these new discoveries will be re-
ported before the Electronics Division and thus The Electro-
chemical Society will play a major role in this field.
In the fluorescent lamp industry, glass tubes are coated by
flushing the tube with a suspension of fluorescent material in
an organic binder and drying and baking. Inspection of these
tubes is shown in Fig. 1. Tungsten coil filaments coated with
electron emitting compounds are sealed into each end and the
(References listed below appear in the Journal or Transactions
of The Electrochemical Society)
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(~ P~dio Corporationof America O WestinghouseElectricCorporation

FIG. 4. A conductive coating heing put on the inside of the FIG. 5. Measuring spectral distribution of light emitted hy
television tube to trap secondary electrons. phosphors in research lab.

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 84C JOURNAL OF THE ELECTROCHEMICAL SOCIETY
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April 1952
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