The effect of Sn for Ti substitution on the average and local crystal structure of BaTi1−xSnxO3 (0 ≤ x ≤ 0.20)

Veselinović, L.; Mitrić, M.; Mančić, L.; Vukomanović, M.; Hadžić, B.; Marković, S.; Uskoković, D.

doi:10.1107/S1600576714007584

The effect of Sn for Ti substitution on the average and local crystal structure of BaTi₁₋_xSn_xO₃ (0 ≤ x ≤ 0.20)

L. Veselinović, M. Mitrić, L. Mančić, M. Vukomanović, B. Hadžić, S. Marković and D. Uskoković

The effect of Sn for Ti substitution on the crystal structure of a perovskite, barium titanate stannate (BTS), BaTi₁₋_xSn_xO₃ for x = 0, 0.025, 0.05, 0.07, 0.10, 0.12, 0.15 and 0.20, was investigated. The powders were prepared by the conventional solid-state reaction technique. The structural investigations of the BTS powders were done at room temperature by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), selected-area electron diffraction (SAED) and Raman spectroscopy analyses. Rietveld refinement of XRD data indicates that gradual replacement of titanium by tin in BaTiO₃ provokes a phase transition from tetragonal for 0 ≤ x ≤ 0.07 to cubic for x = 0.12, 0.15 and 0.20. The coexistence of tetragonal (P4mm) and cubic (Pm $\overline 3$ m) crystal phases was established in powder with nominal composition BaTi_0.9Sn_0.1O₃. The crystal phases determined by Rietveld refinement were confirmed by HRTEM and SAED analyses. The crystal structures of the BTS powders at short-range scale were studied by Raman spectroscopy, which shows tetragonal (P4mm) and a small fraction of orthorhombic (Pmm2) crystal phases for all the examined BTS powders, implying a lower local ordering when compared to the average symmetry.

Keywords: perovskites; phase transitions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600576714007584/ks5409sup1.cif Contains datablocks BT, BTS2.5, BTS5, BTS7, BTS10cubic, BTS10tetragonal, BTS12, BTS15, BTS20
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714007584/ks5409BTsup2.rtv Contains datablock BT
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714007584/ks5409BTS2_5sup3.rtv Contains datablock BTS2.5
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714007584/ks5409BTS5sup4.rtv Contains datablock BTS5
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714007584/ks5409BTS7sup5.rtv Contains datablock BTS7
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714007584/ks5409BTS10sup6.rtv Contains datablock BTS10
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714007584/ks5409BTS12sup7.rtv Contains datablock BTS12
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714007584/ks5409BTS15sup8.rtv Contains datablock BTS15
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600576714007584/ks5409BTS20sup9.rtv Contains datablock BTS20

CCDC references: 995533; 995534; 995535; 995536; 995537; 995538; 995539; 995540; 995541

Computing details top

For all compounds, program(s) used to refine structure: FULLPROF.

(BT) Barium titanate top

Crystal data top

BaTiO₃	c = 4.0338 (1) Å
Tetragonal, P4MM	V = 64.37 (2) Å³
Hall symbol: P 4 -2	Cu Kα radiation
a = 3.9946 (6) Å	T = 295 K

Data collection top

Radiation source: X-ray tube

2θ_min = 20.000°, 2θ_max = 120.000°, 2θ_step = 0.020°

Refinement top

R_p = 11.80	Profile function: pseudo voigt
R_wp = 16.6	10 parameters
R_exp = 6.326	0 restraints
R_Bragg = 8.65	Background function: 6-coefficients polynomial function
5245 data points	Preferred orientation correction: no

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ba	0.00000	0.00000	0.00000	0.0045 (4)*
Ti	0.50000	0.50000	0.488 (4)	0.0022 (6)*
O1	0.50000	0.50000	−0.01 (3)	0.00424*
O2	0.50000	0.00000	0.529 (6)	0.00424*

(BTS2.5) Barium titanate stannate top

Crystal data top

BaTi0.975Sn0.025O₃	c = 4.0245 (8) Å
Tetragonal, P4MM	V = 64.42 (2) Å³
Hall symbol: P 4 -2	Cu Kα radiation
a = 3.9978 (5) Å	T = 295 K

Data collection top

Radiation source: X-ray tube

2θ_min = 20.102°, 2θ_max = 120.002°, 2θ_step = 0.020°

Refinement top

R_p = 8.45	4996 data points
R_wp = 14.4	10 parameters
R_exp = 10.168	0 restraints
R_Bragg = 4.83

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba	0.00000	0.00000	0.00000	0.01203*
Ti	0.50000	0.50000	0.481 (3)	0.00911*	0.97600
Sn	0.50000	0.50000	0.481 (3)	0.00911*	0.02400
O1	0.50000	0.50000	0.002 (3)	0.01404*
O2	0.50000	0.00000	0.5475 (4)	0.01404*

(BTS5) Barium titanate stannate top

Crystal data top

BaTi0.95Sn0.05O₃	c = 4.0188 (1) Å
Tetragonal, P4MM	V = 64.50 (3) Å³
Hall symbol: P 4 -2	Cu Kα radiation
a = 4.0038 (8) Å	T = 295 K

Data collection top

Radiation source: X-ray tube

2θ_min = 20.142°, 2θ_max = 120.042°, 2θ_step = 0.020°

Refinement top

R_p = 9.1	4996 data points
R_wp = 12.2	18 parameters
R_exp = 10.639	0 restraints
R_Bragg = 5.30

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba	0.00000	0.00000	0.00000	0.0085 (4)*
Ti	0.50000	0.50000	0.4848 (9)	0.0069 (6)*	0.94400
Sn	0.50000	0.50000	0.4848 (9)	0.0069 (6)*	0.05600
O1	0.50000	0.50000	−0.008 (3)	0.00580*
O2	0.50000	0.00000	0.523 (2)	0.00580*

(BTS7) Barium titanate stannate top

Crystal data top

BaTi0.93Sn0.07O₃	c = 4.0201 (5) Å
Tetragonal, P4MM	V = 64.56 (3) Å³
Hall symbol: P 4 -2	Cu Kα radiation
a = 4.0075 (5) Å	T = 295 K

Data collection top

Radiation source: X-ray tube

2θ_min = 20.119°, 2θ_max = 120.019°, 2θ_step = 0.020°

Refinement top

R_p = 8.69	5245 data points
R_wp = 11.4	15 parameters
R_exp = 10.137	0 restraints
R_Bragg = 5.55

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba	0.00000	0.00000	0.00000	0.00847*
Ti	0.50000	0.50000	0.4854 (9)	0.00784*	0.934 (2)
Sn	0.50000	0.50000	0.4854 (9)	0.00784*	0.066 (2)
O1	0.50000	0.50000	0.011 (9)	0.00802*
O2	0.50000	0.00000	0.536 (2)	0.00802*

(BTS10cubic) Barium titanate stannate top

Crystal data top

BaTi0.90Sn0.10O₃	V = 64.78 (3) Å³
Cubic, PM3M	Cu Kα radiation
Hall symbol: -P 4 2 3	T = 295 K
a = 4.0164 (2) Å

Data collection top

Radiation source: X-ray tube

2θ_min = 19.828°, 2θ_max = 139.708°, 2θ_step = 0.020°

Refinement top

R_p = 13.9	5995 data points
R_wp = 18.1	20 parameters
R_exp = 17.275	0 restraints
R_Bragg = 11.1

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba	0.00000	0.00000	0.00000	0.01207*
Ti	0.50000	0.50000	0.50000	0.00038*	0.92800
Sn	0.50000	0.50000	0.50000	0.00038*	0.07200
O	0.50000	0.50000	0.00000	0.01356*

(BTS10tetragonal) Barium titanate stannate top

Crystal data top

BaTi0.90Sn0.10O₃	c = 4.0383 (5) Å
Tetragonal, P4MM	V = 64.40 (2) Å³
Hall symbol: P 4 -2	Cu Kα radiation
a = 4.0245 (4) Å	T = 295 K

Data collection top

Radiation source: X-ray tube

2θ_min = 19.828°, 2θ_max = 139.708°, 2θ_step = 0.020°

Refinement top

R_p = 13.9	5995 data points
R_wp = 18.1	20 parameters
R_exp = 17.275	0 restraints
R_Bragg = 7.71

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba	0.00000	0.00000	0.00000	0.00383*
Ti	0.50000	0.50000	0.496 (2)	0.00303*	0.92800
Sn	0.50000	0.50000	0.496 (2)	0.00303*	0.07200
O1	0.50000	0.50000	−0.002 (2)	0.00498*
O2	0.50000	0.00000	0.543 (2)	0.00374*

(BTS12) Barium titanate stannate top

Crystal data top

BaTi0.88Sn0.12O₃	V = 64.94 (1) Å³
Cubic, PM3M	Cu Kα radiation
Hall symbol: -P 4 2 3	T = 295 K
a = 4.0165 (1) Å

Data collection top

Radiation source: X-ray tube

2θ_min = 20.106°, 2θ_max = 120.006°, 2θ_step = 0.020°

Refinement top

R_p = 9.09	4996 data points
R_wp = 11.6	19 parameters
R_exp = 10.118	0 restraints
R_Bragg = 7.13

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba	0.00000	0.00000	0.00000	0.0033 (4)*
Ti	0.50000	0.50000	0.50000	0.0047 (7)*	0.88800
Sn	0.50000	0.50000	0.50000	0.0047 (7)*	0.11200
O	0.00000	0.50000	0.50000	0.0048 (18)*

(BTS15) Barium titanate stannate top

Crystal data top

BaTi0.85Sn0.15O₃	V = 64.87 (3) Å³
Cubic, PM3M	Cu Kα radiation
Hall symbol: -P 4 2 3	T = 295 K
a = 4.0196 (6) Å

Data collection top

Radiation source: X-ray tube

2θ_min = 20.110°, 2θ_max = 120.010°, 2θ_step = 0.020°

Refinement top

R_p = 9.01	4996 data points
R_wp = 11.9	20 parameters
R_exp = 10.168	0 restraints
R_Bragg = 6.91

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba	0.00000	0.00000	0.00000	0.0036 (5)*
Ti	0.50000	0.50000	0.50000	0.0065 (11)*	0.866 (4)
Sn	0.50000	0.50000	0.50000	0.0065 (11)*	0.134 (4)
O	0.00000	0.50000	0.50000	0.016 (2)*

(BTS20) Barium titanate stannate top

Crystal data top

BaTi0.80Sn0.20O₃	V = 65.12 (3) Å³
Cubic, PM3M	Cu Kα radiation
Hall symbol: -P 4 2 3	T = 295 K
a = 4.0247 (5) Å

Data collection top

Radiation source: X-ray tube

2θ_min = 15.232°, 2θ_max = 120.132°, 2θ_step = 0.020°

Refinement top

R_p = 8.84	5246 data points
R_wp = 10.9	19 parameters
R_exp = 9.015	0 restraints
R_Bragg = 7.78

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba	0.00000	0.00000	0.00000	0.0026 (4)*
Ti	0.50000	0.50000	0.50000	0.0072 (6)*	0.82200
Sn	0.50000	0.50000	0.50000	0.0072 (6)*	0.17800
O	0.00000	0.50000	0.50000	0.0049 (16)*

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