John A.

DeLuca
General Electric Corporate Research and An Introduction to Luminescence in
Development Center
P.O. Box 8
Schenectad~,NY 12301 Inorganic Solids

When a solid absorbs vbotons or charzed particles, a Excitation -Absorption-Conversion

number of energy conversion processes are possible, as illus-
trated in Figure 1. One of these processes, luminescence, is Luminescence (T< W C )
used to advantage in such familiar applications as fluorescent
lamps and television screens. We can define luminescence as
the absorption of photons or charged particles by a substance
which is then followed by aphoton emission in excess of that
/ - Photons
VUV-clnfrared
l@&-12.4
124ev+lev
x 10d A

due to thermal apitation (incandescence) and which is stronelv

dependent upon-the nature of the emitting substance (unlike Thermal Processes

\
incandescence). X-rays. Electrons, UV. Visible - monons (-.Ole")
This introdktion to luminescence will treat the class of 0124 A 6 2 0 0 A - motons (T 7 WOOC)
materials which emit characteristic luminescence. These
materials, or phospors, consist of a host material which con- lpev- 2ev ChemicallStructural Change
stitutes the bulk of the phosphor. The characteristic lumi- Flgure I. Ccnversion of Excitation Energy in Solids.
nescence properties are obtained by adding ("doping") to the
host material relatively small amounts of foreign ions. An
activator is a forrign ion which when incorporated intoa host
lattice rives rise to acenter which can be excited to lumines-
cence. A sensitizer is a foreign ion incorporated into a host
lattice and is capable of transferring its energy of excitation
to a neighboring activator, thus inducing luminescence.
Figure 2 is a schematic representation of aphosphor which
contains an activator. The activator creates a center which
a t ~ o r h excitation
s energy and convem it into vlsihle radiation.
'I'he role of a sensitizer is illustrated in Figure 3. It may occur
that an activator with the desired emission does not have a
significant absorption for the a\,ailable exritation energy. In
such a m e it may he possible to use a sensitizer which absorbs
the excitation energy and then transfers this energy to the
activator, which can then emit its characteristic lumines-
cence.
Figure 2. Diagrammatic representation of me role in the luminescenceprocess
Characterization of Phosphors of an activator (A) doped in a host (H) lattice.
Two primary characteristies which are usually determined
for a phosphor are its excitation spectrum and emission
spectrum. We will use the spectra of the phosphor CaFz:Mn2+
to illustrate these determinations. The designation CaFzMn2+
is a short hand notation to indicate that a phosphor has been
obtained by incorporating the activator Mn2+ into a CaFz
host.
A typicalexperimental arrangement for determiningexci-
tation spectra is shown schematically in Figure 4. In this ex-
ample theexcitation source is theoutput of a monochromator
which, like a prism, resolves the exr~tationlight source into

Presented at the ACS National Meeting, March 25,1980, as part

of the State-of-the-ArtSymposium on Solid State Chemistry in the Figure 3. Diagrammatic representation 01 the role in the luminescence pracess
Undergraduate Curriculum sponsored by the Division of Chemical of a sensitizer (S) and ih relationship to an activator (A) and lhe host lattice
Education. (HI.

Volume 57. Number 8. August 1980 1 541

 T
- -- F i l t e r
Selected to
P a s s Emission A's ~ctivstorConcentration
-Absorb Excitation A's
Sample Figure 7. The effenof activator concentration on phosphor efficiency.
F!gm 4. Schematic diagram of a typical experimental anangsment f a recarding
me excitation spechum of a phosphor.

Phosphor
Efficiency

Wawlengfh in Nanomefcrr

Figure 5. The excitation and emission spectrum of Mnz+ in a CaF2 host.

Figure 8. The effect of poison centers on phosphor efficiency

t Fpr
SBiected to I
- Pass Emission A's I
Absorb Excitation A I
Excitation , \ 8W
,
0 2W 400 600
TB
T (Dk)
Figure 6. Schematic diagram of atypical expimental amangemem fw recading
the emission spectrum of a phosphor. Figure 9. The effect of temperature on phosphor efficiency.

its comnonent wavelenzths. The excitation wavelength of
interest illuminates thesample. The intensity of thelumi-
nescence emission is measured by a photomultiplier tuhe. The
optical cutoff filter placed between the sample and the pho-
tomultiplier tube is selected so that it will pass the lumines-
cence emission hut will absorb the reflected excitation ra-
diation. The output of the photomultiplier tuhe is amplified
and then fed into the v axw of an r-v recorder. The value of
the excitation wavelength selected Ls plotted on the x-axis.
Thus. one obtains an x-v . plot
. which shows the intensitv of the
luminescencr emission as a function of the wavelength o i the
rxcitntlun radiation. The excitation swctrum oi the activator
Mn2+ in the host CaFz is shown in Figure 5.
An experimental arrangement for the determination of an
emission spectrum is shown schematically in Figure 6. Usually
a single excitation wavelength is selected. The optical cutoff
filter serves the same purpose as previously descrihed. In this
exneriment the emission of the sample is analyzed by means
ofhamonochromator. The result i s m x-y plot showing the
intensity of the emission as a function of the wavelength of the
emission. The emission spectrum of Mn2+ in CaF2 is also
shown in Figure 5.
Inspertion of Figure 5 illustrates two other important
chararteristics of luminescence emis%ion.It is apparent that
t,he
~ - luminescence
- ~ - ~ ~ ~~ emission
~ - occurs
~ at~loneer~waveleneths
~ ~than ~
the excitation radiation. This is referred to as
the Stokes shift and is more commonlv described bv. savine . ..
that the energy of an emitted photon is usually less than that
of the photon which excited the luminesr~nceOIU,.,~,.,~,. >
h vemission).
The other characteristic noticeable in Figure 5 is that the
peaks in the t!xcitatim spectrum are nut of equal intensity.
'['his occurs hecause the effirienry of con\wsion of the exri-
tation energy into emission energyis not the same for the three
absorption processes that give rise to the three peaks in the
excitation spectrum. The conversion efficiency of a phosphor
is an important consideration in commercial applications. This
efficiencv can he determined and is usuallv. exnressed
. as either
an energy conversion efficiency p~ = Eemitted/Eineident. or a
quantum conversion efficiency pg = Qemitted/Qincident.
Phosphor Phenomena
Like most solid state properties, the luminescence charac-
teristics of a phosphor are dependent upon such factors as the

542 1 Journal of Chemical Education


Re
Bond Distance
Figure 10. Ground state potential energy of a luminescent center in a crystal
lattice with its as~ociatedvibrational states.
Potential
Energy
I as a functinn
Re
Bond Distance
Figure 11. Oround and excited electronic states showing the excitation and
emission processes of luminescence.
composition of the material, the level of purity, and the tem-
perature. These dependencies are reflected in the phenomena
of concentration quenching, poisoning, and thermal
quenching. The graph shown in Figure 7 illustrates concen-
tration quenching. If one has a phosphor consisting of an ac-
tivator incorporated into a host, then one might justifiably
expect the luminescence emission intensity (at a given exci-
tation intensitv) to increase with increases in the activator
concentration. That is, by increasing the activator concen-
tratioli one would he effectively increasina the ahorption of
the incident excitation energy by the phosGhor. ~ e n e d l this
y excited' hy absorbing a quantum of energy, causing it to un.
expected behavior is true at lower concentrations of activator
.-
. 10%).hut as the concentration of activator is increased
is&
still further one finds that there is an optimum concentration
above which the phosphor efficiency actually decreases.
Phosphors can be very sensitive to the presence of foreign
ions other than the beneficial sensitizers and activators. The
effect of these "poisons" or "killers" on phosphor efficiency
is illustrated in Figure 8. If the phosphor is contaminated with
the wrong kind of impurity, it may have only a fraction of its
potential efficiencv. This phenomenon is especiallv important
to keep in mind when ul;dertaking a program t o synthesize
new phosphors. A cavalier attitude toward attention to the
Potential
Energy
I
Re
Bond Distance
Figure 12. Thermal quenching in the configurational Mordlnate model.
details of careful sample preparation can greatly minimize the
chances of discovering a superior phosphor.
Thermal quenching refers to the fact that phosphors are
generally characterized by a transition temperature, Tg,above
which luminescence efficiency decreases rapidly to vanishingly
small values. The phenomenon of thermal quenching is il-
lustrated graphically in Figure 9.
Configurational Coordinate Model of Characteristic
Luminescence
The configurational coordinate model of characteristic lu-
minescence is especially valuable in helping one to gain a
better insight into the various phenomena that we have dis-
cussed so far. The potential energy diagram shown in Figure
10 forms the basis of this model. The potential curve repre-
sents the binding (electronic) energy of an ion in a host lattice
~~~ ~.~~ ~of theinternuclear se~arationbetween it and its
~~ ~~ ~
nearest neighbors. Inn h u n d system the vibrational energy
is uuantized. 'l'he nuantized ril~ra~ional states are indicated
by the levels V, inkigure 10.
Of course. a hound ion mav exist in a number of electronic
states ifsuitably excited from-its lowest or "ground" electronic
state. Each of these states can he represented bv a potential
energy curer and assoviated vibratibnal levels. I n i.'igurr 11
a gruund state and higher "rxcited" state are illuitrated. It
dhould be noted that neithrr the shape ot'the pot~.ntinlenergy
curves nor the position of their minimums (corresponding to
the equilibrium internuclear distance) necessarily coincide.
Using the configurational model as a means of focusing our
thoughts, we'll now use i t to explain the phosphor character-
istics described earlier. The processes of excitation and
emission are illustrated in Figure 11. The hound activator is
~.
dereo a transition from its lowest enerev ... eround
,. state to an
~ ~
~~
rxcited state. Hecause the potential rurves of the two states
are not swnmetrical. the activator "ends UD" in a hiah vihra-
tional state within the excited electronic state. some energy
is lost to the host lattice as vibrational enerw when the excited
state system relaxes to its lowest vibrational level. At this
~ o i n t the
, system returns to its ground electronic state by
givingoff the energy difference as aquantum of luminescence
'Transitions between electronic states of a bound system corre-
spond to quantum energies of photons in theultraviolet through the
visible spectrum.
Volume 57, Number 8,August 1980 / 543
emission. Note that the energy required to excite the system
(length of up arrow) is greater than the energy of the emitted
quantum of energy (length of down arrow). Thus, the model
accounts for the origin of the Stokes Shift in addition to the
excitation and emission process.
Thermal quenching may be explained in this model as il-
lustrated in Figure 12. When there is sufficient thermal energy
available (higher temperatures), the activator, after it has been
excited to an upper vibrational level in the excited electronic
state, can be excited to a still higher vibrational level. In the
illustration in Figure 12 it can be seen that this vibrational
level corresponds to a point of intersection (or equal energy)
between the excited and ground electronic states. Given the
possibility of two paths, the system will seek the path which
allows it to return to its lowest possible energy. Thus, the
system returns to its lowest state by losing energy t o the host
lattice through vibrational transitions. The end result is that
the excitation energy is lost to the lattice and does not con-
tribute to luminescence emission.
As indicated in Figure 11,the rather complicated potential
energy curve and its associated vibrational levels can he rep-
resented simply by a line for each state. The line representa-
tion of the energy states is used in Figure 13 to illustrate the
concept of energy transfer which was introduced earlier in our
definition of a sensitizer (see Figure 3). We see in Figure 13
that a sensitizer is first excited to an upper energy state by
absorbiue the radiation incident on the ~ . h o -s ~ h oThis
r . enerw
of excitation is transferred (sensitizer returns t o its ground
state). bv. excitine a neiahhorine activator which then returns
to its ground Zate with anHccompanying luminescence
emission. This process of transfer is called non-radiative en-
ergy transfer. For it to ?cur, the sensitizer and activator must
have excited state levels of approximately equal energy above
their ground states. Also, the activator and sensitizer must he
close enough in the host lattice for the transfer probability to
he appreciable. Depending upon the mechanism of the
transfer this "close enough" distance may range from 4 to 30
A.
Energy Transfer
Excitation Emission
1 Activator
.w
Figure 13. Schematic diagram illustrating energy t'ansfer between a sensitizer
and activator.
--,.
/
I
Excitation
model.
Transfer
Non-Radiative Dissipation
Figwe 14. An explanation of poisoning in terms of Uw configurational cwtdimte
544 / Journal of Chemical Education
The concept of energy transfer also permits us to gain a
better insight into the phenomenon of poisoning in phosphors.
In Figure 14 is shown the transfer of excitation energy from
a desired site (sensitizer or activator) to a poison site at which
the energy can be lost to the host lattice as vibrational en-
ergy.
Concentration quenching can be understood in this model
by combining the concepts of energy transfer and poisoning.
As we have seen, the necessary conditions for energy transfer
to occur are that the ions involved have excited states of aD-
proximately equal energy and be ut'ficiently close together.
Bs rlrfinition all the activator ions in a ~ h o s ~ h have
o r iden-
tical excited states, and as we increase the concentration of
the activators in the phosphor we create more and more sit-
uations in which the; are close enough for energy transfer to
occur. The result is that a t higher activator concentrations the
energy of excitation can wander throughout the host lattice
from activator to activator until it finds a poison site and is
then lost to the luminescence emission. This process is illus-
trated schematically in Figure 15.
Commercial Applications of Phosphors
Phosphors are important constituents of energy efficient
fluorescent lamps, cathode ray tubes used in televisions, os-
. . and disolavs.
cillosco~es. . - . and in X-rav detectors used in di-
agnostic equipment. Of course not just any phosphur will do
in these anulirnrionr: thus. the solid statc chemist must meet
the challenge of developihg a phosphor with the necessary
properties of a high efficiency for the excitation energy, de-
sired emission spectrum, and long term chemical stability.
I t will be instructive to consider the major application of
phosphors today, their use in fluorescent lamps. The basic
elements of a fluorescent lamp are shown in Figure 16. When
current is passed through the lamp envelope, the gaseous
mercurv atoms are excited to uoner.. enerw -. states which then
return to thr ground itate with an accompanying emission of
radiation. 1)eoendine on the lewl to whirh an atom is excited
it may emit in the visible or in the ultraviolet (2537 A or 1850
\
Fiaure 15. Concentration ouenchina occurs when lhe activator concentration
become5 s ~ l f l cenl) n gh lnat elf cent energy transfer perm ls me exc tslm
energy lo mlgrats mro-gh the how ~ n t l lt strapped at a polson sate
Glass Envelope
rPhosphor
Figure 16. Schematic representation of a fluorescent lamp.
Coating
 Calcium Halophosphate
Gas (PO,), Fx-. CI.. Mn*'. Sb"

Sensitizer Activators
Sb*l Sb"
Mn-

B
ue-l/ Emission
1

Flgue 17. l'k e m i s b n spechum of the commercial flmewem lamp phoaphw.
calcium halophosphate, Cas(P04)sF1-xClx:Mn2+,Sbs+.
A). Most of the emission from the mercuw arc lies in the ul-
traviolet. Consequently, the glass envelope is coated on the
inside with a ohosohor which efficiently - converts the ultra-
violet radiation into visible radiation.
Conditioned as we are to the visible spectrum of the sun, we
would not react favorably to highly efficient lamps with
emission spectra radically different from that spectrum.
Consequently, a fluorescent lamp must contain a phosphor
which provides an emission approximating white light. A
nhosnhor used extensivelv in commercial fluorescent lamos
L .
in calcium halophosphate doped with manganese and ant]-
mony, Cas(P04)3F1,C1,:Mn2+:Sb3+. The emission spectrum
of this phosphor is shown in Figure 17. In this phosphor the
Sb3+ olavs the role both of a sensitizer and an activator and
e s as an activator. The contributions of Sh3+
~ n z ~ h e h a vonly
and Mn2+ are illustrated in Figure 18. The blue emission of
the Sb3+ and the yellow emission of the Mn2+ combine to
produce an emission spectrum that approximates white
light.
In summary, this review has introduced the reader to lu-
Figure 18. The mle of Sb3+ and Mn2+ In the commercial fluorescent lamp
phosphor, celcium halophosphate, C ~ S ( P O ~ ~ F ~ - . C I , : M ~ ~ + : S ~ ~ ~ .
minescence in inorganic materials by first familiarizing him
or her with the terminolow
. of .
. ohosohors.
. We then considered
two basic experimental measurements used to characterize
luminescent solids and described pheoomenologically several
important characteristics of phosphors. The configurational
coordinate model of characteristic luminescence has been
introduced and has been used to eain a better insieht into the
various phosphor phenomena. ~Tnally,we have presented a
brief introduction to a major application of phosphors. It is
hoped that this paper has helped the reader to appreciate the
multidisci~linarvnature of solid state investieations and the
many chalienges"confronting a solid state chemist as he or she
attemots to convert laboratow curiosities into useful prod-
ucts.
Bibliography
Dram.
" . R. S.. "Phvaieal Methods in lnoreanie Chemi8tw," Reinhold Publishing Co.. New
Yark. 1965;chap. 6.
Barrow. G.M. "The SLructurcof Malecules." W . A. Benjamin Ine., New York. 1964.
Lcverenz, H. W., "An Introduction foLumineseenee in Solids,"John Wiley andSon. Inc.,
New York, 1950.
Blsase, G., and Brill. A., "Characteristic Lumin-nee I, 11, and 111," Philips Technical
Revielu.311101 3M, 1970.
Goldberg, P., Editor, "Luminescenee of Inorganic Solids,"Academic Press, New York,
1966.
Garlick, C. F.J., in "Handhueh der Physik." (Editor:Fluge, 8.1 Springer-Verlag. Berlin,
1958. Vol. XXXVI, pp. 1-128.

Volume 57, Number 8. August 1980 / 545