Ab-initio Study on the Correlation of Electric Field

Gradient and Spontaneous Polarization in Hybrid

Improper Ferroelectrics

Samuel S. Santos2, Michel L. Marcondes1*, Ivan P. Miranda1, Pedro

Rocha-Rodrigues2, Lucy V. C. Assali1, Armandina M. L. Lopes2, João P.
Araújo2, and Helena M. Petrilli1
1 Instituto de Física, Universidade de São Paulo, CEP 05508-090, São Paulo, SP, Brazil
3 Institute of Physics for Advanced Materials, Nanotechnology and Photonics, Universidade do Porto, CEP 4169-007, Porto, Portugal

HYPERFINE – 2021

Email: michel@if.usp.br
Motivation
• Dening & Casabela (1980)
$
3 15𝑧%" 9 15𝑧%"
V## = V## + e ( 𝜁% − ' 𝑥𝛿𝑥% + 𝑦% 𝛿𝑦% + & − ' 𝑧% 𝛿𝑧%
𝑟& 𝑟% 𝑟% 𝑟%
%

𝑉!! ∝ 𝑃" If site 𝑖 has inversion symmetry

𝑉!! ∝ 𝑃 If site 𝑖 does not have inversion symmetry

• Gonçalves et al. (2012)

Ø Relation between EFG components and polarization in proper ferroelectrics
Introduction
• Proper Ferroelectrics

𝐹 ∝ 𝑃! + 𝑃%

• Improper Ferroelectrics
𝐹 ∝ 𝑅# 𝑃

• Hybrid Improper Ferroelectrics

𝐹 ∝ 𝑋!" 𝑋#$ 𝑃
Introduction
• Hybrid Improper Ferroelectrics
Cmmm Pmc2(

-P

AA’B2O6
Introduction
• Ruddlesden-Popper structures – An+1BnO3n+7
𝐹 ∝ 𝑋!" 𝑋#$ 𝑃
I4/mmm A2( am
Introduction
• Ferroelectric transition in Ruddlesden-Popper structures
𝐹 ∝ 𝑋!" 𝑋#$ 𝑃
Introduction
• Perturbed Angular Correlation (PAC)
P. Rocha-Rodrigues et al. PRB (2020) DOI: 10.1103/PhysRevB.101.064103
Ca3Mn2O7
 Introduction
• Perturbed Angular Correlation (PAC)
P. Rocha-Rodrigues et al. PRB (2020) DOI: 10.1103/PhysRevB.101.064103
Ca3Mn2O7

Ti-based Mn-based
Ca3Ti2O7 Ca3Mn2O7
CaCd2Ti2O7 CaCd2Mn2O7
Cd3Ti2O7 Cd3Mn2O7
CaCdTi2O6 CaCdMn2O6

Marcondes, M. L. et al., J. Mater. Chem. C (2020) DOI: 10.1039/D0TC03161E

 Results
• Autschbach et al. (2010)
⃗ = 𝑟% 𝑉%+, 𝑟+
𝑓(𝑟) 𝑓 = 𝑟 " 𝑔(𝜃, 𝜙)

• Electric Field Gradient

Ca3Mn2O7 - Mn site

𝑉)) 𝑉** 𝑉!!

Santos, S. S., et al., J. Mater. Chem. C (2021) DOI: 10.1039/d1tc00989c

 Results
• Electric Field Gradient
Ca3Mn2O7 - Ca sites

Ca – rocksalt sites

𝑉))
𝑉**
𝑉!!

Ca – perovskite sites

Santos, S. S., et al., J. Mater. Chem. C (2021) DOI: 10.1039/d1tc00989c

 Results
• Electric Field Gradient
Ca3Mn2O7
Ca - perovskite Ca - rocksalt Mn

𝑉))
𝑉**
𝑉!!

Santos, S. S., et al., J. Mater. Chem. C (2021) DOI: 10.1039/d1tc00989c

 Results
• Electric Field Gradient

Santos, S. S., et al., J. Mater. Chem. C (2021) DOI: 10.1039/d1tc00989c

Summary

• Interchanges between EFG main axis must be taken into account to study the
relation between the EFG and atomic distortions.

• EFG has a quadratic dependence with P even in the presence of complicated

atomic distortions.

• EFG could be used to track transition pathways in hybrid improper ferroelectrics

Ackowledgments
• Profa. Helena Petrilli (USP)
• Profa. Lucy Assali (USP)
• Prof. João Araújo (UP)
• Profa. Armandina Lopes (UP)
• Dr. Samuel Santos (UP)
• Ivan Miranda (USP)
• Pedro Rocha-Rodrigues (UP)
• Estelina da Silva (UP)
FAPESP – 2019/07661-9
More information
Marcondes, M. L. et al., J. Mater. Chem. C (2020) DOI: 10.1039/D0TC03161E

Santos, S. S., et al., J. Mater. Chem. C (2021) DOI: 10.1039/d1tc00989c