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Neutron powder diffraction (NPD) was employed to further investigate the BaTi1−xSnxO3 (BTS) system previously studied by X-ray diffraction. The room-temperature phase compositions and crystal structures of BTS samples with x = 0, 0.025, 0.05, 0.07, 0.10, 0.12, 0.15 and 0.20 were refined by the Rietveld method using NPD data. It is well known that barium titanate powder (x = 0) crystallizes in the tetragonal P4mm space group. The crystal structures of the samples with 0.025 ≤ x ≤ 0.07 were refined as mixtures of P4mm and Amm2 phases; those with x = 0.1 and 0.12 show the coexistence of rhombohedral R3m and cubic phases, while the samples with x = 0.15 and 0.20 crystallize in a single cubic Pm{\overline 3}m phase. Temperature-dependent NPD was used to characterize the BaTi0.95Sn0.05O3 sample at 273, 333 and 373 K, and it was found to form single-phase Amm2, P4mm and Pm{\overline 3}m structures at these respective temperatures. The NPD results are in agreement with data obtained by differential scanning calorimetry and dielectric permittivity measurements, which show a paraelectric–ferroelectric transition (associated with structural transition) from Pm{\overline 3}m to P4mm at about 353 K followed by a P4mm to Amm2 phase transition at about 303 K.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600576716013157/ks5519sup1.cif
Contains datablocks BTS5_0C, BTS5_60C, BTS5_110C, BT, BTS2.5Tetragonal, BTS2.5Orthorombic, BTS5Tetragonal, BTS5Orthorhombic, BTS7Tetragonal, BTS7Orthorhombic, BTS10Cubic, BTS10Rhombohedral, BTS12Cubic, BTS12Rhombohedral, BTS15, BTS20

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS5_0Csup2.hkl
Contains datablock BTS5_0C

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS5_60Csup3.hkl
Contains datablock BTS5_60C

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS5_110Csup4.hkl
Contains datablock BTS5_110C

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS2.5Tetragonalsup5.hkl
Contains datablock BTS2.5Tetragonal

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS2.5Orthorombicsup6.hkl
Contains datablock BTS2.5Orthorombic

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS5Tetragonalsup7.hkl
Contains datablock BTS5Tetragonal

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS7Tetragonalsup8.hkl
Contains datablock BTS7Tetragonal

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS7Orthorhombicsup9.hkl
Contains datablock BTS7Orthorhombic

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS10Cubicsup10.hkl
Contains datablock BTS10Cubic

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS10Rhombohedralsup11.hkl
Contains datablock BTS10Rhombohedral

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS12Cubicsup12.hkl
Contains datablock BTS12Cubic

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS12Rhombohedralsup13.hkl
Contains datablock BTS12Rhombohedral

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS15sup14.hkl
Contains datablock BTS15

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS20sup15.hkl
Contains datablock BTS20

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTsup16.hkl
Contains datablock BT

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600576716013157/ks5519BTS5Orthorhombicsup17.hkl
Contains datablock BTS5Orthorhombic

CCDC references: 1499348; 1499349; 1499350; 1499351; 1499352; 1499353; 1499354; 1499355; 1499356; 1499357; 1499358; 1499359; 1499360; 1499361; 1499362; 1499363

Computing details top

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

(BTS5_0C) top
Crystal data top
Orthorhombic, Amm2c = 5.6615 (9) Å
Hall symbol: A 2 -2V = 127.46 (3) Å3
a = 3.9844 (6) ÅConstant Wavelength Neutron Diffraction radiation
b = 5.6504 (9) Å
Data collection top
Radiation source: nuclear reactor2θmin = 7.470°, 2θmax = 154.199°, 2θstep = 0.050°
Refinement top
Rp = 5.2652936 data points
Rwp = 6.88021 parameters
Rexp = 7.2970 restraints
RBragg = 5.883
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.00949
Ti0.500000.000000.502540.003110.93511
Sn0.500000.000000.502540.003110.06489
O10.000000.000000.489580.00330
O20.500000.250400.245920.00045
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba0.007970.003330.023820.000000.000000.00000
Ti0.001980.033660.022340.000000.000000.00000
Sn0.001980.033660.022340.000000.000000.00000
O10.004660.005160.009420.000000.000000.00000
O20.002920.003480.005050.000000.000000.00290
(BTS5_60C) top
Crystal data top
Tetragonal, P4mmc = 4.0155 (5) Å
Hall symbol: P 4 -2V = 64.29 (1) Å3
a = 4.0012 (5) ÅConstant Wavelength Neutron Diffraction radiation
Data collection top
Radiation source: nuclear reactor2θmin = 7.125°, 2θmax = 153.253°, 2θstep = 0.050°
Refinement top
Rp = 5.2592924 data points
Rwp = 6.84230 parameters
Rexp = 7.3500 restraints
RBragg = 5.937
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.006 (11)
Ti0.500000.500000.52 (15)0.005 (18)0.96466
Sn0.500000.500000.52 (15)0.005 (18)0.03534
O10.500000.500000.01 (3)0.005 (10)
O20.500000.000000.50 (6)0.002 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba0.0050 (12)0.0050 (12)0.01 (3)0.000000.000000.00000
Ti0.002 (2)0.002 (2)0.01 (5)0.000000.000000.00000
Sn0.002 (2)0.002 (2)0.01 (5)0.000000.000000.00000
O10.004 (2)0.004 (2)0.01 (3)0.000000.000000.00000
O20.002 (3)0.0016 (16)0.003 (7)0.000000.000000.00000
(BTS5_110C) top
Crystal data top
Cubic, Pm3mV = 64.25 (1) Å3
Hall symbol: -P 4 2 3Constant Wavelength Neutron Diffraction radiation
a = 4.0052 (4) Å
Data collection top
Radiation source: nuclear reactor2θmin = 7.277°, 2θmax = 153.456°, 2θstep = 0.050°
Refinement top
Rp = 5.3512925 data points
Rwp = 6.92620 parameters
Rexp = 6.8700 restraints
RBragg = 5.442
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.0037 (6)
Ti0.500000.500000.500000.0017 (8)0.94772
Sn0.500000.500000.500000.0017 (8)0.05228
O0.000000.500000.500000.0015 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ba0.0037 (6)0.0037 (6)0.0037 (6)0.000000.000000.00000
Ti0.0017 (8)0.0017 (8)0.0017 (8)0.000000.000000.00000
Sn0.0017 (8)0.0017 (8)0.0017 (8)0.000000.000000.00000
O0.0004 (10)0.0024 (6)0.0024 (6)0.000000.000000.00000
(BT) top
Crystal data top
Tetragonal, P4mmc = 4.030 (3) Å
Hall symbol: P 4 -2V = 64.27 (7) Å3
a = 3.993 (3) ÅConstant Wavelength Neutron Diffraction radiation
Data collection top
Radiation source: nuclear reactor2θmin = 6.724°, 2θmax = 163.873°, 2θstep = 0.050°
Refinement top
Rp = 5.4503144 data points
Rwp = 9.06416 parameters
Rexp = 3.3100 restraints
RBragg = 12.046
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ba0.000000.000000.000000.00268*
Ti0.500000.500000.498070.00413*
O10.500000.500000.009350.01189*
O20.500000.000000.498320.00709*
(BTS2.5Tetragonal) top
Crystal data top
Tetragonal, P4mmc = 4.02526 (6) Å
Hall symbol: P 4 -2V = 64.27 (1) Å3
a = 3.99568 (6) ÅConstant Wavelength Neutron Diffraction radiation
Data collection top
Radiation source: nuclear reactor2θmin = 6.677°, 2θmax = 163.827°, 2θstep = 0.050°
Refinement top
Rp = 6.0553144 data points
Rwp = 7.70023 parameters
Rexp = 5.1020 restraints
RBragg = 5.925
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.00268*
Ti0.500000.500000.473470.00406*0.94978
Sn0.500000.500000.473470.00406*0.05022
O10.500000.500000.011090.00576*
O20.500000.000000.502100.00826*
Barium titanate stannate (BTS2.5Orthorombic) top
Crystal data top
BaTi0.975Sn0.025O3b = 5.6613 (7) Å
Orthorhombic, Amm2c = 5.69249 (17) Å
Hall symbol: A 2 -2V = 128.83 (2) Å3
a = 3.9977 (5) ÅConstant Wavelength Neutron Diffraction radiation
Data collection top
Radiation source: nuclear reactor2θmin = 6.677°, 2θmax = 163.827°, 2θstep = 0.050°
Refinement top
Rp = 6.055RBragg = 13.198
Rwp = 7.70023 parameters
Rexp = 5.1020 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.00611*
Ti0.500000.000000.490850.01806*0.97500
Sn0.500000.000000.490850.01806*0.02500
O10.000000.000000.455870.02353*
O20.500000.250000.250000.01412*
Barium titanate stannate (BTS5Tetragonal) top
Crystal data top
BaTi0.95Sn0.05O3c = 4.02519 Å
Tetragonal, P4mmV = 64.75 Å3
Hall symbol: P 4 -2Constant Wavelength Neutron Diffraction radiation
a = 4.01070 Å
Data collection top
Radiation source: nuclear reactor2θmin = 6.502°, 2θmax = 163.651°, 2θstep = 0.050°
Refinement top
Rp = 5.0923144 data points
Rwp = 6.76022 parameters
Rexp = 4.3770 restraints
RBragg = 6.100
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.00268*
Ti0.500000.500000.498070.00413*0.93677
Sn0.500000.500000.498070.00413*0.06323
O10.500000.500000.009350.01189*
O20.500000.000000.498320.00709*
Barium titanate stannate (BTS5Orthorhombic) top
Crystal data top
BaTi0.95Sn0.05O3b = 5.6810 (3) Å
Orthorhombic, Amm2c = 5.6919 (3) Å
Hall symbol: A 2 -2V = 129.51 (1) Å3
a = 4.00517 (15) ÅConstant Wavelength Neutron Diffraction radiation
Data collection top
Radiation source: nuclear reactor2θmin = 6.502°, 2θmax = 163.651°, 2θstep = 0.050°
Refinement top
Rp = 5.092RBragg = 5.419
Rwp = 6.76022 parameters
Rexp = 4.3770 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.001144 (14)*
Ti0.500000.000000.535 (6)0.002 (4)*0.93677
Sn0.500000.000000.535 (6)0.002 (4)*0.06323
O10.000000.000000.506 (6)0.019 (6)*
O20.500000.254 (3)0.249 (3)0.010 (3)*
Barium titanate stannate (BTS7Tetragonal) top
Crystal data top
BaTi0.93Sn0.07O3c = 4.01953 (2) Å
Tetragonal, P4MMV = 64.54 Å3
Hall symbol: P 4 -2Cu Kα radiation
a = 4.00714 (2) ÅT = 295 K
Data collection top
Radiation source: X-ray tube2θmin = 20.119°, 2θmax = 120.019°, 2θstep = 0.020°
Refinement top
Rp = 9.1645245 data points
Rwp = 12.18915 parameters
Rexp = 10.1370 restraints
RBragg = 5.549
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.00847*
Ti0.500000.500000.4854 (9)0.00784*0.9335 (17)
Sn0.500000.500000.4854 (9)0.00784*0.0665 (17)
O10.500000.500000.011 (9)0.00802*
O20.500000.000000.536 (2)0.00802*
Barium titanate stannate (BTS7Orthorhombic) top
Crystal data top
BaTi0.93Sn0.07O3b = 5.6738 (10) Å
Orthorhombic, Amm2c = 5.6815 (8) Å
Hall symbol: A 2 -2V = 128.99 (4) Å3
a = 4.0013 (7) ÅConstant Wavelength Neutron Diffraction radiation
Data collection top
Radiation source: nuclear reactor2θmin = 6.669°, 2θmax = 163.818°, 2θstep = 0.050°
Refinement top
Rp = 3.806RBragg = 16.188
Rwp = 4.99921 parameters
Rexp = 3.2770 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.00089*
Ti0.500000.000000.499210.01716*0.92212
Sn0.500000.000000.499210.01716*0.07788
O10.000000.000000.476680.00760*
O20.500000.250010.215050.01051*
Barium titanate stannate (BTS10Cubic) top
Crystal data top
BaTi0.90Sn0.10O3a = 4.0166 (5) Å
Cubic, Pm3mV = 64.80 (1) Å3
Hall symbol: -P 4 2 3Constant Wavelength Neutron Diffraction radiation
Data collection top
Radiation source: nuclear reactor2θmin = 6.784°, 2θmax = 163.933°, 2θstep = 0.050°
Refinement top
Rp = 3.6183144 data points
Rwp = 4.54624 parameters
Rexp = 3.7720 restraints
RBragg = 8.294
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.00165*
Ti0.500000.500000.500000.01503*0.90708
Sn0.500000.500000.500000.01503*0.09292
O0.000000.500000.500000.01117
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O0.001290.017400.017400.000000.000000.00000
Barium titanate stannate (BTS10Rhombohedral) top
Crystal data top
BaTi0.90Sn0.10O3c = 6.9563 (9) Å
Trigonal, R3mV = 194.24 (4) Å3
Hall symbol: R 3 -2"Constant Wavelength Neutron Diffraction radiation
a = 5.6782 (7) Å
Data collection top
Radiation source: nuclear reactor2θmin = 6.784°, 2θmax = 163.933°, 2θstep = 0.050°
Refinement top
Rp = 3.618RBragg = 3.222
Rwp = 4.54624 parameters
Rexp = 3.7720 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.01009*
Ti0.000000.000000.494100.02343*0.90357
Sn0.000000.000000.494100.02343*0.09643
O0.500980.499020.001800.01732
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O0.035960.035960.019950.022500.001460.00146
Barium titanate stannate (BTS12Cubic) top
Crystal data top
BaTi0.88Sn0.12O3a = 4.0182 (4) Å
Cubic, Pm3mV = 64.88 (1) Å3
Hall symbol: -P 4 2 3Constant Wavelength Neutron Diffraction radiation
Data collection top
Radiation source: nuclear reactor2θmin = 6.779°, 2θmax = 163.928°, 2θstep = 0.050°
Refinement top
Rp = 4.9443144 data points
Rwp = 6.42129 parameters
Rexp = 5.1900 restraints
RBragg = 6.953
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.00654*
Ti0.500000.500000.500000.01316*0.87463
Sn0.500000.500000.500000.01316*0.12537
O0.000000.500000.500000.01184
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O0.015780.009880.009880.000000.000000.00000
Barium titanate stannate (BTS12Rhombohedral) top
Crystal data top
BaTi0.88Sn0.12O3c = 6.9592 (8) Å
Trigonal, R3mV = 194.50 (4) Å3
Hall symbol: R 3 -2"Constant Wavelength Neutron Diffraction radiation
a = 5.6809 (6) Å
Data collection top
Radiation source: nuclear reactor2θmin = 6.779°, 2θmax = 163.928°, 2θstep = 0.050°
Refinement top
Rp = 4.944RBragg = 2.089
Rwp = 6.42129 parameters
Rexp = 5.1900 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.00458*
Ti0.504660.504660.504660.00798*0.14577
Sn0.504660.504660.504660.00798*0.02089
O0.510760.510760.017330.00963*0.50000
Barium titanate stannate (BTS15) top
Crystal data top
BaTi0.85Sn0.15O3a = 4.0201 (5) Å
Cubic, Pm3mV = 64.97 (1) Å3
Hall symbol: -P 4 2 3Constant Wavelength Neutron Diffraction radiation
Data collection top
Radiation source: nuclear reactor2θmin = 6.761°, 2θmax = 163.910°, 2θstep = 0.050°
Refinement top
Rp = 5.4443144 data points
Rwp = 6.95821 parameters
Rexp = 5.1450 restraints
RBragg = 4.443
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.0098 (9)*
Ti0.500000.500000.500000.0134 (16)*0.83661
Sn0.500000.500000.500000.0134 (16)*0.16339
O0.000000.500000.500000.0106 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O0.0122 (16)0.0098 (9)0.0098 (9)0.000000.000000.00000
Barium titanate stannate (BTS20) top
Crystal data top
BaTi0.80Sn0.20O3a = 4.0241 (5) Å
Cubic, Pm3mV = 65.17 (1) Å3
Hall symbol: -P 4 2 3Constant Wavelength Neutron Diffraction radiation
Data collection top
Radiation source: nuclear reactor2θmin = 6.828°, 2θmax = 158.002°, 2θstep = 0.050°
Refinement top
Rp = 5.8463025 data points
Rwp = 7.35321 parameters
Rexp = 5.3240 restraints
RBragg = 8.003
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ba0.000000.000000.000000.0095 (14)*
Ti0.500000.500000.500000.045 (3)*0.83661
Sn0.500000.500000.500000.045 (3)*0.16339
O0.000000.500000.500000.0136 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O0.016 (2)0.0121 (12)0.0121 (12)0.000000.000000.00000
 

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