J. Ph.vs. Chrm. Solids Vol. 56. No. 2. pp. 261-265.

1995
Copyright #CI 1995 Elsevier Science Ltd
0022-3697(94)00174-x Printed in Great Britain. All rights reserved
0022.3697195 19.50 + 0.00

DEPENDENCE OF LUMINESCENCE OF TITANATES ON

THEIR CRYSTAL STRUCTURE

B. BOUMA and G. BLASSE

Debye Institute, Utrecht University, Postbox 80,000, 3508 TA Utrecht, The Netherlands

(Received 3 June 1994; accepted 16 September 1994)

Abstract-Compounds A,TiOBO, (A = Li, Na; B = Si, Ge) show efficient photoluminescence at room
temperature. The compound LiTiOPO, shows luminescence only below room temperature. The lumines-
cence of BaTiO,, LiTiO, and Na,GeO, are also reported. From the results it is concluded that titanate
octahedra containing a short Tia distance show efficient luminescence at room temperature if these
octahedra are isolated from each other. When the octahedra condense into a framework, the lowest
absorption band shifts to much lower energy, and the Stokes shift and the quenching temperature of the
emission decreases. This is shown for one-, two-, and three-dimensional frameworks of titanate polyhedra.
The effect is ascribed to a broadening of the energy bands.

Keywords: A. optical materials, A. oxides, D. crystal structure, D. luminescence

1. INTRODUCTION The optical measurements were performed by

using a spectrofluorometer Spex Fluorolog, equipped
The luminescence of titanates has been known for a
with two double monochromators and an Oxford
long time [l, 21. In recent years the efficient lumines-
liquid-helium flow cryostat. More details are given in
cence of the species Tia with a short distance
Refs [4,5].
(_ 1.7 A), sometimes called the titanyl group [3,4],
and the luminescence of titanates with broad energy
bands (e.g. TiO*, SrTiO,) [5,6], have been reported 3. RESULTS
as new developments.
3.1. General
Recently some new titanates with such short Tia
distances were reported in the literature, namely The photoluminescence properties of the investi-
A,TiOBO, (A = Li, Na; B = Si, Ge) [7] and gated titanates are summarized in Table 1. Some
LiTiOPO, [8]. They prompted us to extend our literature data are included as well. They all show
previous studies. A special aspect of the present work luminescence spectra consisting of broad bands.
is that we tried to study the influence of oxygen-ion Figures 1 and 2 give some illustrative examples,
sharing of the titanate octahedra with the short Ti+ namely Na,TiOSiO, and BaTiO,. At liquid helium
bond, on the luminescence properties. In fact, this temperature the luminescence quantum efficiencies
sharing has a drastic and harmful influence on the are high. Table 1 shows also the approximate quench-
luminescence of these titanates. ing temperatures of the luminescence. Note especially
that at room temperature the new compounds
AzTiOBO, (A = Li, Na; B = Si, Ge) are efficient
2. EXPERIMENTAL luminescent materials. We will now discuss the results
Compounds were prepared by conventional solid for the individual (groups of) compounds separately.
state techniques. Firing was performed in the air. The
procedures described in Refs [5, 7,8] were used. All 3.2. Compounds A,TiOBO, (A = Li, Na; B = Si,
samples were checked by X-ray powder diffraction Ge)
using CuKcr radiation. Samples LiTiOPO, and Table 1 contains 4 representatives of this family. In
AzTiOBO, (A = Li, Na; B = Si, Ge) showed small NbOPO,, A is vacant and B = P. The compounds
amounts of a second phase, in agreement with the with A = Li, Na are strongly luminescent with a high
reports in the literature. Other samples were single thermal quenching temperature. The crystal structure
phase. All samples investigated in this study are consists of layers of composition TiBO:- bound by
mentioned in Table 1. planes of A+ ions. In the layer there are BO, tetrahe-

261
262 B. BOUMA and G. BLASSE

Table I. Luminescence characteristics of compounds mentioned in the text. Spectral data

at 4.2 K
Excitation Emission Stokes shift
Compound maximum (rim) maximum (rim) (10) cm-‘) Ref.?
Li,TiOSiO, 250 505 20.5 >300 X

Na,TiOSiO, $ 250 490 20 > 300 X

Na,TiOGeO, 255 425 16

a-NbOPO, 260 490 18 > 300
150 ;
LiTiOPO, 275 520 17.5 125 X

NaYTiO, 280 460 14.5 250 x.10

NaLaTiO, 285 480 15 275 x,10
BaTiO, 340 490 9 45
KTiOPO, 335 390 4.5 100 11
K,Ti,O, 280 420 13 > 300 12
TiO, 380 470 5.5 20 x,13
Li,TiO, 300 520 14.5 -250 X

Na, GeO, i 250 410 16 > 300 X

?A cross indicates “this work”. IMeasurements at room temperature.

dra connecting TiO, square pyramids. However, it is 3.3. LiTiOPO,

also possible to consider the titanate group as a
(5 + 1) distorted octahedron. The octahedra form
linear chains perpendicular to the planes. Long and
short Ti-0 distances alternate along the chain.
Table 2 gives several Ti&O distances. It is clear that
the larger the A species, the longer the long Tia
bond, and the more the titanate group is isolated
from other titanate groups.
The compounds Li,TiOSiO, and Na,TiOSiO,
show a luminescence which is similar to that shown
by Ba,TiOSi,O, [18] and Cs,TiOP,O, [4], which also
contain isolated TiOS square pyramids. The com-
pound a-NbOPO, which is in fact isoelectronic
(Nb5+4d0, Ti4+3d0) behaves similarly, but with a
pronounced lower quenching temperature. The
Nb-0 distances (see Table 2) show that in ol-NbOPO,
the niobate groups can no longer be considered as
isolated, since the N&O distances along the chain
direction differ by only OSA. For the titanates this
is 2 1 A.
The compound Na,TiOGeO, has a smaller Stokes
shift than the other members of this family. In
Section 3.5 we will show that this emission is not a
pure titanate emission.
The crystal structure [8] contains chains of corner-
sharing titanate octahedra. The short and the long
Ti-0 distances alternate along the chain. Their differ-
ence is 0.5 8, (see Table 2). The Ti-O-Ti angle is far
from 180”, being about 140”. The luminescences of
c(-NbOP04 and LiTiOPO, are more alike (quenching
temperature!) than those of isostructural cc-NbOPO,
and A,TiOSi04 (A = Li, Na).
3.4. BaTiO,
In the tetragonal phase of BaTiO, the titanate
octahedron has one shorter Ti-0 bond. The differ-
ences are less pronounced than in the titanate
octahedra in Sections 3.2 and 3.3 (see Table 2). The
luminescent properties of BaTiO, are strikingly
different from those for compounds with short Ti-0
bonds: the absorption edge is at more than
10,000 cm-’ lower energy, the Stokes shift is very
small, and the quenching temperature is low (see
Table 1). This shows that we are dealing with a
completely different situation. In fact, the results for
BaTiO, are very similar to those for SrTiO, [5, 19,201,
thus we assume that their luminescence is related to
the three-dimensional corner sharing of the titanate
octahedra (perovskite structure). Therefore the fact

qr

200
1 400 600nm
Fig. 1. Emission and excitation spectra of the luminescence 300 600 nm
of Na,TiOSiO, at 4.2 K. @ indicates the radiant power per
constant wavelength interval, qr the relative quantum out- Fig. 2. Emission and excitation spectra of the luminescence
put, both in arbitrary units. The excitation wavelength is of BaTiO, at 4.2 K. The excitation
. . wavelength
..__ is 345 nm, the
250 nm, the emission wavelength monitored 490 nm. emisston wavelength momtored 485 nm.
 Luminescence of titanates 263

Table 2. Some crystallographic data of compounds under investigation

Ti-0 distance

(Average)
Compound Short one Long one others Remarks? Ref.

Li,TiOSiO, 1.70 2.70 1.97 isolated 7

Na,TiOSiO, 1.70 3.41 1.99 isolated 7
Na,TiOGeO, 1.72 3.44 2.0 isolated 7
a -NbOPO, 1.78 2.32 1.97 I-D 7
LiTiOPO, 1.70 2.23 2.02 I-D 8
BaTiO,(tetr.) 1.86 2.17 2.00 3-D 14
KTiOPO, $ 1.7211.74 2.16/2.10 1.98/2.00 I-D 15
K,Ti,Os 1.57 - - 2-D 16
NaLnTiO, - - - 2-D 17
tSee also text. n-D means n-dimensional framework of titanate polyhedra.
JKKOPO, has two crystallographically different titanate octahedra.

that BaTiO, has an even stronger distorted modifi-
cation at the temperatures where the luminescence
occurs [14] does not seem to be of importance.
3.5. Na,GeO,
An impurity observed in the preparation of
Na,TiOGeO, was Na,GeO, . For this reason we
prepared the latter in pure form and found it to show
a very intense luminescence at 300 K (see Table 1).
Figure 3 shows the emission spectra of Na,GeO, and
Na,TiOGeO,. The two emissions are different. The
luminescence of Na,GeO, is ascribed to charge-
transfer transitions in the germanate group [21,22].
This implies that in Na,TiOGeO, the titanate and
the germanate groups have absorption levels at about
equal energy, which complicates the situation con-
siderably. The emission spectrum of Na,TiOGeO,
shows most probably germanate as well as titanate
emission (compare Figs 1 and 3).
3.6. Li,TiO,
For the same reason as in the case of Na,GeO,, we
investigated L&TiO, . This compound has an ordered
rocksalt structure in which titanate octahedra share
edges forming a two-dimensional network 1231.The
absorption edge of Li,TiOS is at much lower energy
(_ 6000 cm-‘) than for the isolated titanate groups
(see Table 1).
0
3.1. Results from the literature
Table 1 contains also a number of results taken
from the literature, viz:
-NaYTiO, and NaLaTiO, [17] in which the
titanate octahedra show one short Ti-0 distance and
two-dimensional corner sharing. The titanyl bond is
perpendicular to the titanate planes. In our study we
could confirm the luminescence results reported
before [lo].
--KTiOPO, [ 11, 151,with a linear zig-zag chain of
titanate octahedra which show corner sharing (50%
cis, 50% tmns). Figure 1 in the recent Ref. [24]
gives a nice picture of these chains. The low-energy
position of the absorption edge and the small Stokes
shift of the emission are remarkable.
-TiOz (rutile) 1131, with a three-dimensional
titanate network of a complicated nature. We could
repeat the earlier reported results with a free-exciton
line and self-trapped exciton emission.
4. DISCUSSION
The optical transition involved in the titanate
luminescence is due to a “charge-transfer” transition,
although it is nowadays realized that the term charge-
transfer is incorrect, since the transition involves a
reorganization of electronic charge on titanium as
well as an oxygen without a considerable amount of
real charge transfer [2].
Investigations by Van der Waals and coworkers on

A
isoelectronic species have shown that the excited state
is highly complicated [25]. For this reason we do not
1 2 discuss the nature of the transitions any further.
t Hazenkamp et al. [26] have shown by calculation
that the short bond in polyhedra of da ions is directly
involved in the luminescence, confirming the con-
clusion from experimental results [3].
LOO 600nm
In order to discuss the influence of the relative
Fig. 3. A comparison of the emission spectra of Na,GeO,
(1) and Na,TiOGeO, (2) at 4.2 K. Excitation wavelength is orientation of titanate groups, we follow an approach
250 nm. described elsewhere [5,6]. In the case of an isolated
264 B. BOUMA and G. BLASE
group, the configurational coordinate diagram is
valid yielding a large Stokes shift due to a consider-
able relaxation in the excited state. However, if the
titanate groups are coupled in such a way that wave
function overlap can occur, energy band broadening
takes place, resulting in a lower-energy absorption
edge, a smaller Stokes shift, and lower quenching
temperatures. In TiO, free-exciton emission could
even be observed.
In the present investigation Li2TiOSi04 and
Na,TiOSiO, are clearly the systems with the most
isolated titanate polyhedra. This is not only based
on structural data (the extremely long sixth Ti-0
distance), but also on the luminescence results
(high absorption energy, large Stokes shift, high
quenching temperature). As observed before, the
Stokes shift of the linear TiX emission is larger than
that of the regular titanate octahedron [2]. Up till
now there is no explanation for this fact. In
cr-NbOPO1 this isolated character is lost and the
luminescence properties change: the absorption shifts
somewhat to lower energy, the Stokes shift is re-
duced, and the quenching temperature has decreased.
The chains in LiTiOPO, are similar to those in
a-NbOPO, in spite of the difference in crystal struc-
ture. As is to be expected, the luminescence properties
are similar.
The way in which the titanate octahedra in
KTiOPO, share edges to form a linear chain is
obviously very favourable for wavefunction overlap.
The absorption shifts to considerably lower
energy, the Stokes shift becomes very small
and the quenching temperature is low. The relation
between these effects and the presence of strong
second-harmonic-generation has been pointed out
[ll, 271.
Now we turn to two-dimensionally connected
titanate groups. Consider first the recently
reported K,Ti,O, [12]. The authors consider this
compound to be built up from trigonal bipyramidal
units. However, in view of the structure determi-
nation [16], this is incorrect. The structure contains
titanate layers consisting of square pyramidal TiO,
groups. The short TiGO distance is to the apex and is
perpendicular to the layer. The layers are built up by
edge sharing and corner sharing. Obviously this
occurs in a way which is not too favourable for
wavefunction overlap, since the absorption edge
remains at relatively high energy and the quenching
temperature seems to be high judging from
Ref. [12].
In NaLnTiO, the situation is comparable, although
here titanate octahedra condense into layers by edge
sharing only. The luminescence characteristics of
NaLnTiO, and K,Ti,O, are very similar. Due to the
short Tia distance perpendicular to the titanate
plane, the Ti“+ ions reside above and under the
central oxygen layer [ 171.In Sr2Ti04 they reside in the
oxygen layer and immediately the absorption edge
shifts to longer wavelength (330 nm), the Stokes shift
reduces to 11,000 cm-‘, and the quenching tempera-
ture to about 100 K [28]. This seems to indicate that
it is mainly the off-plane position of titanium in
K,Ti,O, and NaLnTiO, which counteracts the
energy-band broadening.
Two-dimensional Li,Ti03 shows only edge sharing
of titanate octahedra. The amount of delocalization
lies in between that in the case of Sr,TiO, and that
in the case of K, Ti, 0, and NaLnTiO, .
Three-dimensional titanate coupling occurs in the
perovskites SrTiO, and BaTiO, and in the rutile
TiO*. This favours energy band formation resulting
in a low-energy absorption edge, small Stokes shift
and low quenching temperature (see Table I), as
discussed already elsewhere [5, 61. In this connection
we note that the isolated titanate octahedron in
BaZrO, :Ti has its first absorption band at 290 nm, its
emission band at 430 nm, so that the Stokes shift is
about 12,000 cm-’ [29], pointing to considerably less
delocalization.
The data in Table 1 suggest further a relation
between the position of the lowest absorption band
and the value of the Stokes shift. Large Stokes shifts
occur only for high-energy absorption. This agrees
with the model used.
The influence of oxygen-ion sharing on the
luminescence of titanates as presented here, is
shown for niobates by one sole compound, cesium
niobium phosphate. This compound can be obtained
in two different modifications with different lumines-
cent properties [30]. One can be written as CsNb-
OP,O,; it contains a Nb-0 group with short distance
(1.72 A), and shows a luminescence similar to that of
A,TiOSiO, (A = Li, Na). The other can be written as
CsNb(PO,),; it contains regular niobate octahedra,
its absorption edge is at more than lO,OOOcm-
lower energy, and it does not luminesce, not even at
4.2 K.
5. CONCLUSION
Compounds with isolated titanate octahedra with
a short Ti-0 distance show efficient luminescence
with a large Stokes shift and short-wavelength ultra-
violet excitation. When the titanate octahedra
become more and more connected, the quenching
temperature of the luminescence decreases consider-
ably, whereas the lowest absorption band shifts
drastically to lower energy. These effects are ascribed
to broadening of the energy bands.
 Luminescence of titanates 265

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