Download citation
Download citation
link to html
Characterizing the crystalline disorder properties of heterovalent ternary semiconductors continues to challenge solid-state theory. Here, a Landau theory is developed for the wurtzite-based ternary semiconductor ZnSnN2. It is shown that the symmetry properties of two nearly co-stable phases, with space groups Pmc21 and Pbn21, imply that a reconstructive phase transition is the source of crystal structure disorder via a mixture of phase domains. The site exchange defect, which consists of two adjacent antisite defects, is identified as the nucleation mechanism of the transition. A Landau potential based on the space-group symmetries of the Pmc21 and Pbn21 phases is constructed from the online databases in the ISOTROPY software suite and this potential is consistent with a system that undergoes a paraelectric to antiferroelectric phase transition. It is hypothesized that the low-temperature Pbn21 phase is antiferroelectric within the c-axis basal plane. The dipole arrangements within the Pbn21 basal plane yield a nonpolar spontaneous polarization and the electrical susceptibility derived from the Landau potential exhibits a singularity at the Néel temperature characteristic of antiferroelectric behavior. These results inform the study of disorder in the broad class of heterovalent ternary semiconductors, including those based on the zincblende structure, and open the door to the application of the ternaries in new technology spaces.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053273320003095/ug5001sup1.cif
Contains datablocks global, Pca21, Pmc21, Pmn21, Pna21

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053273320003095/ug5001sup2.pdf
The setting transformations from Pna21 to Pbn21 and from Pca21 to Pbc21

CCDC references: 1988421; 1988422; 1988423; 1988424

Computing details top

(Pca21) top
Crystal data top
Orthorhombic, Pca21c = 5.580000 Å
a = 5.850000 ÅV = 220.67 Å3
b = 6.760000 Å
Data collection top
h = l =
k =
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzBiso*/Beq
Zn10.083500.875000.00000
N10.083500.875000.37500
Sn10.083500.625000.50000
N20.083500.625000.12500
(Pmc21) top
Crystal data top
Orthorhombic, Pmc21c = 5.580000 Å
a = 3.380000 ÅV = 110.33 Å3
b = 5.850000 Å
Data collection top
h = l =
k =
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzBiso*/Beq
Zn10.000000.833500.00000
N10.000000.833500.37500
Sn10.500000.666500.50000
N20.500000.666500.12500
(Pmn21) top
Crystal data top
Orthorhombic, Pmn21c = 5.580000 Å
a = 3.380000 ÅV = 110.33 Å3
b = 5.850000 Å
Data collection top
h = l =
k =
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzBiso*/Beq
Zn10.000000.416500.50000
Sn10.000000.083500.00000
N10.000000.416500.87500
N20.000000.083500.37500
(Pna21) top
Crystal data top
Orthorhombic, Pna21c = 5.580000 Å
a = 5.850000 ÅV = 220.67 Å3
b = 6.760000 Å
Data collection top
h = l =
k =
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzBiso*/Beq
Zn10.083500.125000.00000
N10.083500.125000.37500
Sn10.083500.375000.50000
N20.083500.375000.12500
 

Follow Acta Cryst. A
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds