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with the absence of green PL in Tb doped CaTiO3.36,37 In structural parameters of the host stannates are summarized in
addition, the enhancement of the PL intensity in CaSnO3:Tb, Table 1. The CaSnO3:Tb and SrSnO3:Tb samples exhibited
CaZrO3:Tb, and CaZrO3:Eu was observed by Mg codop-
ing,38−40 which markedly contrasts with the decrease of the PL Table 1. Crystal Structural Parameters of AeSnO3 (Ae = Ca,
intensity in Y3Al5O12:Tb by Mg codoping.41 However, the Sr, Ba)
occupying sites of Tb ions and their valence states are not fully
CaSnO3 SrSnO3 BaSnO3
understood, and the origin of the Mg codoping effect is still
unknown. In this study, the XAFS measurements of the Tb LIII space group Pbnm (No. 62) Pbnm (No. 62) Pm3m̅ (No. 221)
edge in Tb doped perovskite-type stannates and zirconates crystal system orthorhombic orthorhombic cubic
were carried out to understand the detailed states of doped Tb tolerance factora 0.927 0.961 1.018
ions and their luminescence properties. site symmetry (A) m m m3̅m
distortion indexb (A) 0.141 0.084 0.000
2. EXPERIMENTS a
Tolerance factor: t =
rA + rO
.r ,r , and rO are ionic radii of A and
2 (rB + rO) A B
The samples were prepared by a conventional solid state reaction
B site cations and oxide ion, respectively.
method using starting materials of AeCO3 (Ae = Ca, Sr, Ba) and MO2 1 n |l − l |
b
(M = Sn, Zr) for host materials and Tb4O7 and MgCO3 for dopant. Distortion index: Dl = n ∑i = 1 i l av . n, lav, and li are the number
av
Both Tb and Mg ions were substituted for Ca ions at A sites in of neighboring oxide ions and averaged bond length between central
nominal composition; the Tb concentration was 0.5 at. % at A sites, cation and coordinated oxide ions and the ith individual bond length,
and Mg ions were substituted for Ca ions at 3.0 at. %. Although the Tb respectively.
concentration is rather small and disadvantageous to the XAFS
measurements, the optimal concentration for Tb3+ luminescence in the
stannate samples was adopted because of its sharp concentration green luminescence due to the 4f−4f electronic transition from
quenching. The starting materials were mixed thoroughly with ethanol, the 5D4 to 7FJ states in Tb3+ ions. The luminescence intensity in
and the dried mixed powders were heated at 1400 °C for 6 h in air to the CaSnO3:Tb was higher than that in the SrSnO3:Tb. In
obtain the samples. contrast, the green luminescence was not observed in the
The XRD patterns of the obtained samples were measured using an
BaSnO3:Tb. Because the 4f−4f transition is originally forbidden
XRD diffractometer (Rigaku, RINT-2500), and crystalline phases in
the samples were identified. As a result, it was confirmed that each at a crystal site with an inversion center, Tb3+ luminescence will
sample was composed of a pure perovskite-type phase. The PL spectra be influenced by the local structure of the A site in the host
of the samples were measured using a conventional spectrofluorometer perovskite structure. In the Ca and Sr stannate samples,44 the
(Jasco, FP-6500). The XAFS spectra of the Tb LIII edge were site symmetry at the A site is m without an inversion center,
measured at the BL14B2 beamline of the SPring-8 synchrotron and the local structure is distorted as shown in the inset in
radiation facility. Perovskite-type TbAlO3 and AeTbO3 (Ae = Sr, Ba) Figure 1.
with the space group Pbnm (No. 62) were used as reference samples to The degree of distortion from an ideal cubic perovskite
examine the occupying sites and the valence of Tb ions. The reference structure is frequently evaluated by the tolerance factor.45−47
samples were also prepared by a solid state reaction with the same
The tolerance factors of the Ca and Sr samples with
heating conditions. The fluorescence XAFS measurements using a 19-
element Ge solid state detector were carried out on the samples doped orthorhombic distortion were 0.927 and 0.961, respectively,
with dilute Tb ions, while the standard XAFS measurements using the and they largely differed from the ideal value of 1.0 for a cubic
gas-flow-type ionization chambers were made on the reference perovskite structure. The distortion index is also useful to
samples. The crystal structures of samples were visualized using the estimate the degree of local distortion around a cation.48,49 To
VESTA code,42 and the obtained XAFS spectra were analyzed using compare the local distortion at A sites straightforwardly in
the IFEFFIT code.43 AeSnO3 (Ae = Ca, Sr, Ba), 12 Ae−O bond lengths at A sites
were used for the distortion index evaluation. The distortion
3. RESULTS AND DISCUSSION indexes at A site in the Ca and Sr samples were 0.141 and
3.1. Tb Occupying Sites and Tb Valence. Figure 1 shows 0.084, respectively, which largely deviated from zero. The
PL spectra of Tb doped alkaline earth stannates, AeSnO3:Tb values of the tolerance factors and distortion indexes indicated
(Ae = Ca, Sr, Ba), and local crystal structures at A sites. Crystal that the influence of the distortion on Tb ions doped in the Ca
sample is much larger than that in the Sr sample. This
difference probably caused the higher PL intensity in the Ca
sample. In the Ba sample, the crystal system is cubic, and the
site symmetry at the A site is m3̅m with an inversion center. In
addition, the tolerance factor of 1.018 is very close to 1.0, and
the distortion index is zero. These parameters clearly verified
that the Ba sample is an ideal cubic perovskite structure. It is,
therefore, reasonable to consider first that the 4f−4f transitions
in Tb ions were strongly forbidden in the Ba sample, which
resulted in the absence of the green luminescence.
To examine the local structures of Tb ions directly, XAFS
spectra of the Tb LIII edge were measured in AeSnO3:Tb (Ae =
Ca, Sr, Ba). The X-ray absorption near edge structures
Figure 1. PL spectra and photographs of Tb doped alkaline earth (XANES) of the Tb LIII edge of the samples are shown in
stannates, AeSnO3:Tb [Ae = Ca (), Sr (···), Ba (---)], and local Figure 2 with those of the reference samples. The reference
crystal structures of A sites, in which each Ae ion is located in the samples of TbAlO3 and AeTbO3 (Ae = Sr, Ba), which are
center and blue and white balls are Sn and O ions, respectively. The orthorhombic perovskite-type structures, are isostructural with
samples were excited by UV irradiation at 254 nm. each other and also with the Ca and Sr samples. Although the
B DOI: 10.1021/acs.inorgchem.7b02165
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article
D DOI: 10.1021/acs.inorgchem.7b02165
Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry Article
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.7b02165.
Summary of Tb3+:Tb4+ and additional ionic radius
information (PDF)
■
occupying sites in BaTiO3:Dy3+ by Mg codoping was observed
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F DOI: 10.1021/acs.inorgchem.7b02165
Inorg. Chem. XXXX, XXX, XXX−XXX