Uaterials ResearchBulletin, Vol. 30, No. il. pp.

1359-1362, 1995
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THE LWlbW+JESCENCE
OF B?+ IN LaInO, AND SOME OTHER PEROVSKITES

LI. van Steensel, S.G. Bokhove, A.M. van de Craats, J. de Blank and G. Blasse*
Department of Solid State Chemistry, Debye Institute, Utrecht University,
Postbox 80000,3508 TA Utrecht, The Netherlands

(Received June 26,199s; Refereed)

ABSTRACT
The composition LaInO,:Bi” shows an efficient photoluminescence at room
temperature. The results are compared to those for other perovskites. Coval-
ency, coordination number, and site symmetry appear to be important factors
for the luminescence characteristics of the Bi3’ ion.

MATERIALS INDEX: A, oxides; D, luminescence

INTRODUCTION

The luminescence of the Bi3+ion has been investigated in many host lattices (l-3). Due to the
volatility of B&O, some obvious host lattices have not been investigated. Only recently, for
example, the luminescence of Bi’+ in the garnet structure has been reported by using hot-
pressing techniques (4). Another lack in the literature is the luminescence of Bi” in oxidic
perovskites. Compounds with perovskite structure often serve as model compounds in the
study of physical properties of solids. Only Witzman et al. (5) reported the luminescence of
CaZrO,:Bi”, as far as we are aware.
In an extended study on the influence of In3+ions on the Bi3+luminescence (6,7) which
sometimes appears to be detrimental, we found that LaInO,:Bi’+ is a very efficient blue-emit-
ting luminescent material. Its properties, together with those of a few related compounds, are
the topic of this paper.

EXPERIMENTAL

Samples were prepared by usual solid-state techniques (8). The bismuth concentration was
weighed as 1 mole percent. Final firing temperatures were 1200°C (LaInO,) and 1250°C

1359
1360 L.I. VAN STEENSELet al. Vol. 30, No. 11

TABLE I
Some Data on the Bi’+Luminescence in Oxidic Perovskites

Excitation Emission
maximum maximum Stokes shift
Composition (W (nm) ( 103cm-‘) T; (ref.)

LaInO,:Bi’+ 340 420 6 4.2 K

CaZrO3’.Bi3’ -320 390 -6 300 K, (5)

LaA10,:Bi3’ 285 375 9 300 K

CaZrO,:Pbz+ 285 365 8 4.2 K; (10)

LaInO, 260 515 19 4.2 K

(LaAlO,). All samples were checked by X-ray powder diffraction using CuKa radiation. They
are single-phase distorted perovskites (LaAIO, rhombohedral, LaInO, orthorhombic).
The optical measurements were carried out as described before (9).

RESULTS

Table I surveys the results obtained, together with some literature data. All spectra consist of
broad bands, the maxima of which are given in the table. Fig. 1 shows the emission and exci-
tation spectra of the efficient blue luminescence of LaIn0,:Bi3’. The light output of LaAIO,:
Bi3’ is lower, but this may be due to a lower bismuth concentration due to higher firing tem-
peratures which promote volatilization of B&O,.
Undoped LaInO, shows a weak luminescence with a very large Stokes shift. The excitation
maximum corresponds to the onset of the reflection minimum in the diffise reflection spec-
trum. This shows that excitation occurs into the LaInO, host lattice.
Decay measurements were performed for LaInO,:Bi”. All decay curves are exponential.
The temperature dependence of the decay time is given in fig. 2. The curve is typical of a Bi3+
ion. The data can be fitted to a three-level scheme, yielding 500 cm-’ for the energy difference
between the two excited states (3P, and ‘P,) (3). The decay time at 4.2 K is 965 ps CP, - IS,
transition).

DISCUSSION

The undoped LaInO, shows a weak green luminescence. Several In” compounds are nowa-
days known to luminesce: ho, (1 l), InJi,O, and In,Ge,O, (12), and In,TiO, (13), for exam-
ple. The I$ ion can also act as a luminescent centre: CaO:In3’ (14) . The optical transition
involved seems to be a charge-transfer transition (14,15). The low luminescence intensity of
LaInO, at 4.2 K and the low energy transfer rate from LaInO, to the Bi3+ion suggests that the
excited state of LaInO, is rather mobile, so that it can easily reach quenching centres. Since
Vol. 30, No. 11 BISMUTH LUMINESCENCE 1361

FIG. 1.
i!L
400
0
t

500 nm

The emission and excitation spectra of the luminescence of LaInO,:Bi at 4.2 K (right and lefi hand
side, respectively). Excitation wavelength 335 run, monitored emission wavelength 425 nm. Q
indicates the relative quantum output, @ gives the radiant power per constant wavelength interval,
both in arbitrary units.

the InO, octahedra are sharing comers building a threedimensional sublattice, the energy
levels can easily broaden into energy bands. This accounts for the excited state mobility (8).
Let us now turn to the Bi’+ ion. Table I shows that the excitation maximum of the Bi’+ lu-
minescence: shifts to longer wavelengths, i.e. lower energies, in the series LaAlO,, CaZrO,,
LaInO,. This nephelauxetic effect in the ‘S, -t 3P, excitation transition points to an increasing
covalency in the same sequence (8,16). That the noble-gas perovskite LaAlO, yields the more
ionic surroundings for Bi3+is obvious. The higher covalency in LaInO, can be understood as
follows. The:2p-oxygen orbitals pointing to Bi” are involved in x bonding to the octahedrally
coordinated ions (Zr4’ 4d0, In’+ 4d”). The d” ions are less able to form n bonds than the do
ions (17,lS). This implies that the Bi-0 bonds in LaInO, can have a higher degree of coval-
ency, since the oxygen orbitals involved are less polarized by the octahedral ions than in
CaZrO,.
Table I shows that the degree of covalency results only in a spectral shift, but not in a drastic
change in luminescence. The same is true if we consider Pb*+ also (see table I). The Stokes

11 . *

D
i=
t
a5 11
00 100 200 K

FIG. 2.
Temperature dependence of the decay time of LaInO,:Bf+. Excitation wavelength 335 run. The
solid curve presents the fit to a three-level scheme.
1362 L.I. VAN STEENSEL et al. Vol. 30, No. 11

shift is of the same order of magnitude. The somewhat larger value for Bi3’ in LaAlO, may be
ascribed to the higher coordination number in the perovskite structure: whereas the rhombo-
hedrally distorted perovskites offer the larger cation an effective nine- or higher coordination,
the orthorhombically distorted ones offer an effective eight coordination (19). The smaller
Stokes shift of the latter ones results in a very efficient luminescence: LaInO,:Bi” (this work)
and CaZr03:Bi3’ (5).
This dependence on coordination number has been well documented (20). It is illustrated
here by the cases of CaO:Bi’+(six coordination, Stokes shift 2.10’ cm-‘, ref. 2 1). and of the S,
site in Y,O,:BT’ (six coordination, Stokes shift 2.103 cm”, refs 2 and 7). However, a low
coordination in itself is not sufIIcient for a small Stokes shift, as shown by the C, site in Y,O,:
Bi3+ (six coordination, Stokes shift 9.103 cm-‘, refs 2 and 7) and La,O,:Bi” (seven coordi-
nation, Stokes shift 11.1 O3cm-‘, ref. 2). The Bi3+ion should also be coordinated in a sym-
metrical way, so that the s* effect (off-centre position) cannot occur (20). This is actually the
case in the perovskite structure, where the sublattice of edge-sharing octahedra offers a more
or less symmetrical coordination to the larger ions, even if the site is slightly distorted.
Finally we note that the AE value, i.e. the ‘P, - ‘P,, energy difference, observed for Bi3+in
LaInO,, is well in line with a relation between the Stokes shift and the value of AE, which has
been reported earlier (20).
In conclusion, LaInO,:Bi” is an efficient, blue-emitting photoluminescent material. Its
luminescence characteristics can be understood from earlier observations,

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