J. Phys. Chem. So&is Vol. 53, No. 5, pp. 677480. 1992 @X2-3697/92 SS.00 + 0.

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Printed in Great Britain. Q 1992 F=ergsmon Press pk

LUMINESCENCE OF Eu3 +-DOPED LANTHANUM

TITANATE (La,TiO,), A SYSTEM WITH
ONE-DIMENSIONAL ENERGY MIGRATION
J. ALARCON? and G. BLASSE~
tDept. de Quinica Inorganica, Universitat de Valencia, 46100 Burjassot (Valencia), Spain
$Debye Research Institute, Utrecht University, POB 80.000, 3508 TA Utrecht, The Netherlands

(Received 9 August 1991; accepted 23 October 1991)

Abstract-The titanate and Eu 3+ luminescence of a composition La,TiO,-Eu are reported as a function

of temperature. At 4.2 K the quantum efficiency is very high, because the titanate excitation energy is
localized. At 300 K there is delocalization and quenching centres are easily reached, so that the quantum
efficiency becomes low. This is discussed in terms of the crystal structure, as are the peculiarities of the
ELI’+ spectra.
ICeywords: Luminescence, La,TiO, , Eu3 + .

1. INTRODUCTION with instruments described before [3]. The sample

Eu3 +-activated phosphors are applied widely for
lighting and display [l]. Their physical properties
have been intensively studied. We were tempted to
investigate the Eu3 + luminescence in La,TiOS, be-
temperature could be varied between liquid helium
temperature (LHeT) and room temperature (RT).
3. RESULTS

cause the crystal structure of this host lattice has
some remarkable characteristics. Although the for-
mula La,TiO, suggests that the trigonal bipy~madai
Ti05 groups in this structure do not share oxygen
ions, this is not the case, since one of the oxygen ions
is coordinated by La3+ only [2]. The TiO, groups
form linear chains along the c-axis by sharing apexes
resulting in an arrangement 0-Ti-O-Ti-0 with
Ti+Ti angles close to 180”. Such an arrangement is
expected to promote strong interaction between the
titanate groups, with SrTiOj as the most famous
example. In SrTiO, the coupling of the titanate
groups is three-dimensional, in La2Ti05 it is one-
dimensional.
Because of this structural property it seemed
worthwhile to investigate the luminescence of
La,TiO,-Eu, and to compare the results with those
for other host lattices in which energy migration is
known to occur.
2. EXPERIMENTAL
Starting materials were Laz03 (99.99%), Eu203
(99.9%) and TiOz ( > 99.9%). Intimate mixtures were
fired at final temperatures of 1300°C. The products
were found to be single phase using X-ray powder
diffraction. In this paper we present results for the
compositions La,., Eu,, TQ and nominally pure
La,TiO, . The optical measurements were performed
The diffuse reflection spectra (at RT) show an
optical absorption edge at about 290 nm which can be
ascribed to the titanate absorption. Apart from very
weak features due to Eu3+ in the europium contain-
ing sample, the visible region shows a weak and
broad absorption band for wavelengths < 500 nm.
This absorption is ascribed to transition metal ions
present as an impurity in the starting material TiOz.
Such absorption bands are well known in titanates
and have been ascribed to charge-transfer transitions
[4]. Using the Kubelka-Munk formula, the concen-
tration of the impurities is estimated to be 700 ppm.
This is in good agreement with the data of the
supplier.
At 300 K the undoped sample does not luminesce
at all, the 5% Eu3+ sample shows under ultraviolet
excitation a weak red emission with a quantum
efficiency of a few per cent. At 4.2 and 78 K the
samples show a strong near-white emission for short
wavelength U.V. excitation, and a red emission for
long wavelength U.V. excitation. The quantum
efficiency of the former was estimated to be some
80% at 4.2 K.
Figure 1 shows the emission spectrum of the Eu3+
emission in La,TiO,. It consists of the well-known
3Do-‘F, transitions. At shorter wavelengths the
emission lines from the ‘D# = 3, 2, I) level could
also be observed. Their intensity is about two orders
of magnitude lower than the intensity of the 3D,

677
678 J. ALARCON
and G. BLA~~E
600 700nm
Fig. 1. Spectral energy distribution of the 5D0-7F, emission
of Eu3+ in La,TiO, at LHeT. Excitation at 391 nm
(7F0-5L6). The value of J is indicated.
emission lines. They are a factor of two weaker for
titanate excitation than for Eu3+ excitation at
395 nm.
Figure 2 shows the excitation spectrum of the Eu’+
emission of La, TiO,-Eu’ + at LHeT. The broad band
in the U.V. corresponds with the optical absorption
observed in the reflection spectrum and is, therefore,
due to titanate excitation. This shows that energy
transfer from titanate to europium takes place. The
sharp lines are the intraconfigurational transitions of
the 4f6 configuration of the Eu3+ ion. At room
temperature the ultraviolet band is much weaker
relative to the lines. The difference is more than one
order of magnitude, corresponding to the difference
in quantum efficiency at the two temperatures.
The inset of Fig. 2 shows the excitation line
corresponding to the ‘F,-‘D, transition of the Eu’+
ion. It shows also vibronic transitions on the shorter
wavelength side [5]. Due to the large splitting of the
electronic lines, it is hard to analyse the vibronic lines
exactly, but it is clear that there are a more intense
group at about 250 cm-’ and a less intense group at
about 750 cm-’ from the electronic lines. The former
are ascribed to coupling with the Eu-0 vibrational
stretching mode, the latter to coupling with the Ti-0
--A
44 L60nm
300 SOOnm
Fig. 2. Excitation spectrum of the Eu’+ emission of
La,,,Eu,,,TiO, at LHeT. qr gives the relative quantum
output. The inset gives the 7F0-5D, excitation transition
stressing the vibronic transitions.
stretching mode. In tungstates and molybdates these
groups have usually comparable intensities (Ref. 5
and references cited therein).
Excitation into the titanate at LHeT yields not
only Eu3+ emission, but also broad band titanate
emission [6]. Their integrated intensity ratio is about
1:2. At RT this titanate emission is quenched.
The spectra of La,TiO, consist of broad bands
only. The emission band has its maximum at about
475 nm, the excitation band is the same as for Eu3+
with a maximum at about 280 nm. Upon increasing
the temperature, the emission intensity started to
drop above 40 K and is quenched above 150 K.
4. DISCUSSION
4.1. The Eu3+ emission
The lines in the Eu’+ spectra are well known and
do not need a further assignment. At first sight there
seems to be a discrepancy between the very low site
symmetry (C,) and the number of possible sites for
the lanthanide ion (two) on one hand, and the very
simple emission spectrum which, in good approxi-
mation, shows two lines for the ‘D,,-‘F, and for the
5Do-7F, transitions. However, not only are the two
independent sites very much alike [2], but also
the seven coordination of the lanthanide ions can be
considered as an octahedral one elongated along
a trigonal axis, to which a seventh ion has to be
added at somewhat larger distance. The trigonally
distorted octahedron is then responsible for the
splitting into two levels of the ‘F, level and into three
levels of the ‘F2 level (approximate site symmetry
D,&. This symmetry allows two lines for both
transitions, explaining the emission spectrum in first
approximation.
The seventh ion lowers the symmetry to the real
one, viz. C,. This ion causes a linear crystal field on
the Eu3+ ion, a necessary condition for the obser-
vation of the ‘Do-‘F, transition with the observed
intensity. It will also bring about a further crystal
field splitting. From the emission spectrum it is clear
that the longer wavelength components of the
5Do-7F,,, transitions are not single lines at all. In this
way the experimental emission spectrum agrees com-
pletely with the crystallographic data [2]. Simul-
taneously it is a nice illustration of the fact that small
changes in the surroundings of the Eu’ + ion influence
the intensities much stronger than the crystal field
splittings [7].
Apart from sharpening which makes small split-
tings better observable, there is no essential difference
between the Eu3 + excited Eu3 + luminescence at RT
and LHeT. Especially the luminescence intensity
 Luminescence of Eu’+-doped lanthanum titanate
does not vary with temperature. This is completely
different for titanate excitation. But first we discuss
the titanate luminescence itself.
4.2. The titanate luminescence
Titanate luminescence involves charge-transfer
transitions [6]. This luminescence has been observed
for tetrahedral, octahedral and tetragonal pyramidal
titanate groups. To this we now add the trigonal
bipyramidal titanate group. At LHeT the quantum
efficiency of the luminescence is high, but it starts to
drop above 40 K.
There are two models to explain this decrease. The
first is the appearance of non-radiative transitions in
the titanate group which compete with the radiative
transitions. In this model all transitions occur in one
and the same titanate group. This model is always
valid for diluted systems. The second model considers
energy transfer between titanate groups, so that the
excitation energy can migrate to quenching centres.
Here the excitation gets lost non-radiatively.
By diluting the concentration of luminescent ions
it is possible to distinguish between the two models
[8]. Unfortunately, this is not possible in the case of
La,TiO, in view of the specific titanium coordination.
Therefore we compare our system with results from
the literature on other compounds with an aim to
solve our problem in this way.
An important fact to start with is the observation
that the optical absorption of islolated titanate
groups is usually situated at about 250 nm, i.e. some
40,000 cm-’ [6, 8, 91. In La,TiO, its position is
N 35,000 cn-I, which indicates interaction between
the titanate groups via the linear Ti&Ti bridge.
Due to band broadening the absorption energy
is reduced [lo]. This interaction extends in one
direction. In Sr,TiO, it does so in two dimensions
and the absorption band is at N 30,000 cm-’ [1 11.
In SrTiO,, finally, the connections are three-
dimensional and the absorption band is at only
N 27,000 cm-’ [12]. Although it cannot be excluded
that the relevant bond distances and angles in these
compounds are slightly different, the enormous shift
must, in our opinion, be ascribed in the first place
to the interaction between titanate groups and its
dimensionality.
The stronger the interaction, the less the relaxation
in the excited state [lo, 121. This is measured by the
Stokes shift of the emission. Interestingly enough, the
Stokes shift decreases with increasing dimensionality
of the interaction: La,TiO, 14,000 cm-‘, Sr*TiO,
11,000 cm-’ (1 l), and SrTiO, 8000 cm-’ [12].
At LHeT the emission of these titanates can be
ascribed to self-trapped exciton emission on one of
619
the titanate groups. The mobility of the excitons can
be neglected. The SrTiO, emission already starts to be
quenched above 10 K. De Haart et al. [12] have
shown that the exciton becomes mobile and reaches
impurities. In the case of SrTiO,: CIJ+ the Cr’+
emission builds up at the expense of the titanate
emission.
Therefore we ascribe the quenching of the lumines-
cence of La,TiO, above 40 K to exciton migration to
quenching sites. Probably these consist of the impu-
rity transition metal ions (see above). Since these are
expected to be built into the chain, they can be
effective quenchers of the titanate emission.
Finally we note that in LaWO,Cl (13),
La,NbO,Cl, and La,TaO,Cl, (14) there are linear
W04, Nb04 and Tao, chains of exactly the same
constitution as the TiO, chain in La,TiO,. The
luminescence of these compounds [13,14] is very
similar to that of La,TiO,.
4.3. Titanate-Eu3 + energy transfer in
La, TiO, : Eu’ +
First we consider the situation at LHeT: the quan-
tum efficiency of the total luminescence upon titanate
excitation is high and the emission comprises one-
third of Eu3+ emission.
If the excitation remains localized on the excited
titanate group, the ratio of titanate to Eu3+ emission
intensity can be derived as follows. Each titanate
group in La, TiO, has eight nearest La3 + neighbours.
With a Eu3+ concentration of 5% the probability to
find eight La’+ ions around the TiOs group in
La,,VEu,,,TiO, is 0.95’ = 0.66. Since it is very prob-
able that the excited titanate group transfers to Eu3 +
if there is a Eu3+ ion on one of the eight nearest
neighbour sites [15], this simple model predicts for
La,,gEu,,, TiOS upon titanate excitation at LHeT 34%
Eu3+ and 66% titanate emission, in excellent agree-
ment with experiment. This confirms the self-trapped
exciton model suggested above.
Since the titanate emission band is so broad, all
higher emitting levels of the Eu3+ ion are populated
by the transfer process. This explains why the amount
of higher level emission from Eu3+ is higher for ‘Ls
excitation than for titanate excitation, since the latter
also populates the lower levels.
Now we consider the quenching region. Since
quenching starts above 40 K due to linear exciton
migration and the quenching site concentration
( _ 650 ppm) is nearly two orders of magnitude lower
than the Eu’+ concentration (SO!), it is clear that
trapping of the mobile exciton by the quenchers must
be much more effective than trapping by the Et?+
680 J. ALARCONand G. BLASE
ions. Also the hopping time of the exciton must be
shorter than the transfer time to EL?+. An important
factor is undoubtedly the fact that the quenchers are
situated in the linear titanate chain (see above),
whereas the Eu’+ ions are not. Further we note that
the oxygen in the Ti-O-T&-O-Ti chain is the seventh
oxygen of the La’+ coordination mentioned above,
i.e. it is the one with the largest La3+a2- distance.
For the smaller Eu’+ ion this may be even more
pronounced. Since this type of transfer is assumed to
occur by exchange [15], the titanate-Eu’+ transfer
may be relatively slow, although faster than the
radiative decay time of the TiO, group. Also the weak
vibronic coupling of the Eu’+ transitions with the
titanate vibrations points to a relatively weak inter-
action. We are planning further investigations on this
one-dimensional system.
Acknowledgement-J. A. thanks D. G. I. C. Y. T. of the
Spanish Ministry for Education for financial support.
REFERENCES
1. Blasse G. (Ed.), Mat. Chern. Phvs. 16, (1987): Chem.
Mater. 1, i94 (i989).
2. Guillen M. and Bertaut E. F., C. R. AC. Sci. Paris, B262,
962 (1966).
3. Hazenkamp M. F., Blasse G. and Sabbatini N., J. Phys.
Chem. 95. 783 (1991).
4. Blasse G.; Suucrure and Bonding 76, 153 (1991).
5. Blasse G., Znorg. Chim. Acta 169, 33 (1990).
6. Blasse G., Structure and Bonding 42, 1 (1980).
I. Blasse G., Chem. Phys. Letters 20, 573 (1973).
8. Kroger F. A., Some Aspects of the Luminescence of
Solids, Elsevier, Amsterdam (1948).
9. Macke A. J. H., J. Solid State Chem. 18, 337
(1976).
10. Blasse G., Progr. Solid State Chem. 18, 19 (1988).
11. Macke A. J. H., Thesis, University of Utrecht
(1976).
12. de Haart L. G. J., de Vries A. J. and Blasse G. J. Solid
Stale Chem. 59, 291 (1985).
13. Blasse G., Bokkers G., Dirksen G. J. and Brixner L. H.,
J. Solid State Chem. 46, 215 (1983).
14. Blasse G., Lammers M. J. J., Verhaar H. C. G., Brixner
L. H. and Torardi C. C., J. Solid State Chem. 60, 258
(1985).
15. Powell R. C. and Blasse G., Structure and Bonding 42,
43 (1980).