TY - JOUR
T1 - Probing Cation Displacements in Antiferroelectrics
T2 - A Joint NMR and TEM Approach
AU - Ding, Hui
AU - Egert, Sonja
AU - Huang, Binxiang
AU - Jiang, Tianshu
AU - Carstensen, Leif
AU - Šić, Edina
AU - Liu, Yucheng
AU - Yang, Tongqing
AU - Groszewicz, Pedro Braga
AU - More Authors, null
N1 - Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.
PY - 2023
Y1 - 2023
N2 - High-resolution scanning transmission electron microscopy (STEM) enjoys great advantages for atomic-resolution visualization of the atomic structure, while failing to disclose structural information along the atomic columns. On the other hand, solid-state nuclear magnetic resonance (NMR) spectroscopy is highly sensitive to the three-dimensional, local structure around atoms in the bulk sample but typically cannot provide an intuitive visualization of the structure. Thus, the combination of atomic-resolution (S)TEM and solid-state NMR spectroscopy has the potential to establish an in-depth, multidimensional structural understanding. Here, we explore this novel strategy to probe the structure of antiferroelectric perovskite oxides PbZrO3 and (Pb,La)(Zr,Sn,Ti)O3. We combine complementary information regarding the in-plane displacement vector mapping from STEM with the analysis of local PbO12 environments from 207Pb NMR spectroscopy to provide unprecedented insight into Pb displacements. For PbZrO3, an ordered 4-fold in-plane displacement modulation is clearly revealed via STEM imaging; meanwhile, the out-of-plane information is provided by two discrete 207Pb NMR signals attributed to two crystallographic Pb sites in the 2D-PASS NMR spectrum. In the chemically modified (Pb,La)(Zr,Sn,Ti)O3 system, disorder of the structure manifests in not only an inhomogeneous displacement modulation but also a broad distribution of 207Pb chemical shifts, related to significant disorder of displacement magnitudes and a favoring of larger displacements. We show that the displacement distribution depends on whether both in-plane and out-of-plane displacements or only out-of-plane displacements are considered. Our findings demonstrate the advantages in the structural analysis using combined TEM and NMR approaches, hence laying the foundation work for controlling and optimizing functional properties.
AB - High-resolution scanning transmission electron microscopy (STEM) enjoys great advantages for atomic-resolution visualization of the atomic structure, while failing to disclose structural information along the atomic columns. On the other hand, solid-state nuclear magnetic resonance (NMR) spectroscopy is highly sensitive to the three-dimensional, local structure around atoms in the bulk sample but typically cannot provide an intuitive visualization of the structure. Thus, the combination of atomic-resolution (S)TEM and solid-state NMR spectroscopy has the potential to establish an in-depth, multidimensional structural understanding. Here, we explore this novel strategy to probe the structure of antiferroelectric perovskite oxides PbZrO3 and (Pb,La)(Zr,Sn,Ti)O3. We combine complementary information regarding the in-plane displacement vector mapping from STEM with the analysis of local PbO12 environments from 207Pb NMR spectroscopy to provide unprecedented insight into Pb displacements. For PbZrO3, an ordered 4-fold in-plane displacement modulation is clearly revealed via STEM imaging; meanwhile, the out-of-plane information is provided by two discrete 207Pb NMR signals attributed to two crystallographic Pb sites in the 2D-PASS NMR spectrum. In the chemically modified (Pb,La)(Zr,Sn,Ti)O3 system, disorder of the structure manifests in not only an inhomogeneous displacement modulation but also a broad distribution of 207Pb chemical shifts, related to significant disorder of displacement magnitudes and a favoring of larger displacements. We show that the displacement distribution depends on whether both in-plane and out-of-plane displacements or only out-of-plane displacements are considered. Our findings demonstrate the advantages in the structural analysis using combined TEM and NMR approaches, hence laying the foundation work for controlling and optimizing functional properties.
UR - http://www.scopus.com/inward/record.url?scp=85179098083&partnerID=8YFLogxK
U2 - 10.1021/acs.chemmater.3c02045
DO - 10.1021/acs.chemmater.3c02045
M3 - Article
AN - SCOPUS:85179098083
SN - 0897-4756
VL - 35
SP - 10041
EP - 10049
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 23
ER -