HIGHLIGHT

Inorganic Luminescent Materials:

100 Years of Research and Application
By Claus Feldmann,* Thomas Jüstel, Cees R. Ronda,
and Peter J. Schmidt

Up until approximately 80 years ago, only black-body radiation (including natural sources)
was available to illuminate our environment. To realise state-of-the-art lamps, TV sets,
monitors, and medical scanners, took an enormous scientific and technical effort. Inorganic
luminescent materials are key components, which were, are, and will be prerequisite to the functionality and success of many
lighting and display systems. In this Highlight, a hundred years of inorganic luminescent material research are reviewed.

Luminescent materials (or phosphors) are gener-

ally characterized by the emission of light with ener-
gy beyond thermal equilibrium. More vividly this
means: The nature of luminescence is different from
that of black-body radiation. Luminescence can oc-
cur as a result of many different kinds of excitation,
which is reflected in expressions such as photo-, elec-
tro-, chemi-, thermo-, sono-, or triboluminescence. In
practice, most often the excitation is via X-rays, cath-
ode rays, or UV emission of a gas discharge. The role
of the phosphor is to convert the incoming radiation into visi-
ble light. In addition to the type of excitation, two other terms
are used quite often to classify luminescent materials. Both can
be related to the decay time (s): fluorescence (s < 10 ms) and
phosphorescence (s > 0.1 s).[1]
The luminescence of inorganic solids, which is the focus of
this contribution, can be traced to two mechanisms: lumines-
cence of localized centers and luminescence of semiconductors
(Fig. 1).[1,2] The first case is represented by transitions between
energy levels of single ions (e.g., f±f transitions of Eu3+ in
Y2O3:Eu3+) or complex ions (e.g., the charge-transfer transition
on [WO4]2± in CaWO4). In the case of luminescent centers, the
transition rate is (more or less strongly) correlated to the rele-
vant quantum-mechanical selection rules, and reflected in the
intensity as well as the decay time of the transition. Excitation
and emission can be (as shown in Fig. 1) both localized to one
center (e.g., [WO4]2± in CaWO4) or separated from each other:
excitation on sensitizer (e.g., Ce3+ in LaPO4:Ce3+,Tb3+) is fol-
± tensify the luminescence, indicating that impurity-type lumi-
[*] Dr. C. Feldmann, Dr. T. Jüstel, Prof. C. R. Ronda, Dr. P. J. Schmidt
Philips Research Laboratories
D-52066 Aachen (Germany)
E-mail: claus.feldmann@philips.com
Prof. C. R. Ronda
Utrecht University, Ornstein Laboratory
P.O. Box 80 000, NL-3408 TA Utrecht (The Netherlands)
Fig. 1. Schemes illustrating the underlying physical processes of luminescence on isolated cen-
ters (left, middle) and in semiconductors (right).
lowed by emission on activator (e.g., Tb3+ in LaPO4:Ce3+,Tb3+).
Consequently, energy transfer between sensitizer and activator,
for instance due to dipole±dipole, multipole±multipole, or ex-
change interaction is required for the latter case. Luminescence
of semiconductors (also in Fig. 1) normally occurs, after band-
to-band excitation, between impurity states within the bandgap
(e.g., donor±acceptor pair luminescence in ZnS:Ag+,Cl±).
Closely related is also the underlying mechanism of inorganic
electroluminescence, which recently gained a lot of interest for
the realization of light-emitting diodes (LEDs).
Inorganic luminescent materials have been known since ap-
proximately the tenth century in China and Japan as well as
since the end of the middle ages in Europe.[3,4] The first materi-
als were found in nature (e.g., naturally doped willemite, schee-
lite, or calcite crystals). Around 1600, the Stone of Bologna at-
tracted Galilei's interest (Table 1). This barite mineral emits
yellow to orange light with long persistence when subjected to
sunlight. Without knowing the physical processes, Galilei
excluded mystery as origin of the phenomenon. In 1671, by
heating the mineral with carbon black, Kirchner was able to in-
nescence of BaS, and not BaSO4, is the origin of light emis-
sion.[5] Luminescent materials these times were only used for
decorative purposes. At the end of the nineteenth century, a
first major milestone concerning luminescent materials and de-
vices was the realization of gas discharges and electron beams

Adv. Funct. Mater. 2003, 13, No. 7, July DOI: 10.1002/adfm.200301005 Ó 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 511